CN115504457A - Method for preparing large-diameter single-walled carbon nanotube by using biomass silicon-based catalyst - Google Patents
Method for preparing large-diameter single-walled carbon nanotube by using biomass silicon-based catalyst Download PDFInfo
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Abstract
The invention provides a method for preparing a large-diameter single-walled carbon nanotube by using a biomass silicon-based catalyst. The experimental procedure was as follows: (1) catalyst preparation: the method comprises the steps of carrying out water washing, acid leaching, washing, drying, roasting, ball milling and other treatment modes on silicon-containing biomass such as rice hulls to prepare nano-scale biomass silicon dioxide, and further carrying metal to prepare a biomass silicon-based catalyst, wherein the catalyst has a rich mesoporous structure with the aperture smaller than 4 nm. (2) synthesis of single-walled carbon nanotubes: ethanol is used as a carbon source, hydrogen is used as a reducing gas, argon is used as a shielding gas, and the catalyst with the cobalt content of 1wt% can selectively synthesize the large-diameter single-walled carbon nanotube by adopting a chemical vapor deposition method under the conditions that the reducing temperature is 700 ℃ and the growth temperature is 900-1000 ℃. The biomass silicon-based catalyst prepared by the invention can be used for selectively synthesizing single-walled carbon nanotubes with large tube diameters (larger than 2 nm).
Description
Technical Field
The invention relates to a method for preparing a large-diameter single-walled carbon nanotube by using a biomass silicon-based catalyst.
Background
The structure (chirality, tube diameter, etc.) of the single-walled carbon nanotube determines the unique physical and chemical properties thereof, and greatly influences the practical application of the single-walled carbon nanotube in the fields of composite materials, electronics, optoelectronics, biology, medicine, etc. The typical tube diameter distribution of the single-walled carbon nanotube is between 0.7 and 2nm. Large-diameter single-walled carbon nanotubes (> 2 nm) have great advantages in many advanced applications compared to small-diameter carbon tubes. For example, large-diameter single-walled carbon nanotubes have higher carrier mobility, better nanotube contact, and faster response time, and are therefore promising materials for electronic devices. In addition, according to theoretical research, the large-diameter single-walled carbon nanotubes have stronger capillary force for absorbing liquid. Meanwhile, the optical fiber has the inner surface volume suitable for guest molecule encapsulation, and has great application prospect in the fields of multispectral imaging and optical conversion devices. However, the single-walled carbon nanotubes obtained in practical production processes generally have a broad distribution of chirality and tube diameter, so that their application in these particular fields is limited. Therefore, it is very necessary to obtain a sample enriched with large-diameter single-walled carbon nanotubes (> 2 nm).
Previous research has been directed to obtaining large-diameter single-walled carbon nanotube enriched samples by controlled growth or post-synthesis separation methods. Over the past decade, several methods including density gradient ultracentrifugation, conjugated polymer encapsulation, aqueous two-phase extraction and gel permeation chromatography have shown excellent ability to separate and enrich large-diameter single-walled carbon nanotubes. However, these methods have limitations, such as that the separation method always requires the introduction of surfactants or polymers which are difficult to separate and remove, the purity and yield of the obtained single-walled carbon nanotubes are relatively low, and the separation process is complicated, time-consuming and expensive. Therefore, the direct synthesis of the sample enriched in the large-diameter single-walled carbon nanotube is not only beneficial to subsequent separation, but also can effectively reduce the application cost.
The chemical vapor deposition method is widely applied to the tube diameter selective synthesis of the single-walled carbon nanotube due to the advantages of simple operation, low reaction temperature, easy control of the synthesis process and the like. In the method, the catalyst is crucial to the pipe diameter distribution of the single-walled carbon nanotube. At present, many researches are carried out to selectively synthesize single-walled carbon nanotubes with relatively large tube diameters (about 1.2 nm) by using catalysts prepared by using silica as carriers. However, the chemical synthesis of these commercial silicas is expensive and environmentally hazardous and also requires harsh synthesis conditions.
The biomass has the advantages of low price, reproducibility, wide distribution and the like, part of siliceous biomass materials can be used as natural sources of silicon dioxide, such as rice hulls, straws, corn stalks, sorghum stalks, oats, barley, rice chaff or sorghum hulls, and a large amount of silicon dioxide in the siliceous biomass materials can be extracted by calcining after certain pretreatment steps. However, these biomasses are typically discarded as agricultural waste. Therefore, the research and development of the catalyst based on the biomass silicon-based carrier for the selective synthesis of the large-caliber single-walled carbon nanotube has important research significance.
Disclosure of Invention
The invention aims to develop a load type catalyst based on a silicon-containing biomass carrier and is used for the growth of a large-diameter single-walled carbon nanotube.
In order to achieve the aim, the invention designs the experimental processes of preparation of the biomass silica supported catalyst for synthesizing the large-diameter single-walled carbon nano tube by the chemical vapor deposition method, determination of relevant synthesis conditions and the like, and the experimental processes comprise the following steps:
(1) Obtaining biomass silicon dioxide: carrying out pretreatment steps such as washing, acid leaching, firing, ball milling and the like on silicon-containing biomass such as rice hulls to obtain a biomass silicon dioxide carrier;
(2) Preparing a biomass silicon-based catalyst: one or more transition metal salt solutions and the biomass silicon dioxide carrier obtained in the step (1) are prepared by soaking, stirring, aging, drying, grinding, roasting and other treatment modes;
(3) Synthesizing the large-diameter single-walled carbon nanotube: and (3) synthesizing the large-diameter single-wall carbon nanotube material by using the catalyst obtained in the step (2) through an ethanol chemical vapor deposition method.
Preferably, the biomass material selected in the step (1) is one or a mixture of more of rice hulls, straws, corn stalks, sorghum stalks, oats, barley, rice chaff or sorghum hulls.
Preferably, the acid solution adopted in the acid leaching process in the step (1) is sulfuric acid, hydrochloric acid, nitric acid or ionic liquid, the acid leaching temperature is 20-60 ℃, and the acid leaching time is 30min-2h.
Preferably, the burning temperature in the step (1) is 300-800 ℃, and the burning time is 3-12h.
Preferably, the rotation speed of the ball milling in the step (1) is 300-600r/min, and the ball milling time is 2-72h.
Preferably, the transition metal salt used in step (2) is one or more selected from metal salts containing iron, cobalt, nickel, copper, molybdenum, vanadium, etc. Preferably, the cobalt salts selected are cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt acetate and cobalt oxalate, the catalyst containing a total loading of transition metal elements in the range of from about 0.5wt% to about 10wt%.
Preferably, the solvent used in the step (2) is ethanol, methanol and dichloromethane, the roasting temperature of the catalyst is 100-800 ℃, the roasting time is 3h, and the heating rate is 2 ℃/min.
Preferably, the catalyst dried, ground and calcined in step (3) is used for synthesizing the carbon nanotube by a chemical vapor deposition method under the conditions that the reduction temperature is 500-900 ℃, the growth temperature is 900-1000 ℃ and the growth time is 3-60min, the inert atmosphere is argon or nitrogen, the flow rate of the inert atmosphere is 30-100sccm, the reduction atmosphere is hydrogen, the flow rate of the hydrogen is 100-200sccm, and the flow rate of the ethanol gas is 300-700sccm.
The invention successfully utilizes the rice hull and other silicon-containing biomass wastes to prepare a biomass silicon-based catalyst, and adopts an ethanol chemical vapor deposition method to use the catalyst, wherein the reduction temperature is 500-900 ℃, the growth temperature is 900-1000 ℃, the growth time is 3-60min, the inert atmosphere is argon, the flow rate of the argon is 30-100sccm, the reduction atmosphere is hydrogen, the flow rate of the hydrogen is 100-200sccm, and the flow rate of the ethanol gas is 300-700sccm, so that a large-diameter single-walled carbon nanotube enriched carbon nanotube sample is successfully synthesized. The invention has certain significance for the controlled synthesis of the large-diameter single-walled carbon nanotube.
Drawings
FIG. 1 shows N in the catalyst obtained in example 1 2 Adsorption and desorption isotherms.
FIG. 2 is an X-ray diffraction spectrum (XRD) of the catalyst obtained in example 1.
FIG. 3 is a UV-vis-diffuse reflectance spectrum (UV-vis-DRS) of the catalyst obtained in example 1.
FIG. 4 shows a temperature programmed reduction curve (TPR) of the catalyst obtained in example 1.
Fig. 5 is a Raman spectrum (Raman) of the carbon nanotube obtained in example 3.
FIG. 6 is an ultraviolet-visible-near infrared (UV-vis-NIR) spectrum of the carbon nanotube obtained in example 3.
FIG. 7 is a Transmission Electron Microscope (TEM) image of the carbon nanotube obtained in example 3.
FIG. 8 is a distribution diagram of the tube diameters of the carbon nanotubes obtained in example 3.
Fig. 9 is a Scanning Electron Microscope (SEM) image of the carbon nanotubes obtained in example 3.
Detailed Description
The present invention will be described in detail below with reference to specific examples, but the purpose and purpose of the description of the embodiments are merely to illustrate the present invention, and the present invention is not limited to the actual scope of the present invention in any form, and the present invention is not limited to the scope of the present invention.
Example 1
(1) Preparation of biomass silicon dioxide: washing rice hulls with water to remove surface soluble impurities, and drying in an oven at 60 ℃ for 24 hours; then soaking the rice hulls in a sulfuric acid solution (0.5 mol/L) at 60 ℃, continuously stirring for 30min on a magnetic stirrer at the rotating speed of 300r/min, then washing with deionized water for multiple times, filtering until the filtrate is neutral, and drying in an oven at 60 ℃ overnight; putting the dried sample in a muffle furnace under an air atmosphere, and burning for 6h at 600 ℃ to obtain silicon dioxide; and ball-milling the obtained silicon dioxide coarse particles in a ball mill for 24 hours at a speed of 500r/min to obtain the catalyst carrier biomass silicon dioxide.
(2) Preparation of the catalyst: dissolving cobalt (II) acetylacetonate with a certain mass by using a dichloromethane solution with a certain volume, slowly adding the cobalt (II) acetylacetonate solution into the biomass silica carrier, placing the mixture on a magnetic stirrer, stirring for 30min, then heating to 60 ℃, continuously stirring until no excess solvent exists, placing the mixture in a drying oven for drying at 60 ℃, grinding the dried sample into powder, and roasting in a muffle furnace at 450 ℃ for 3h to obtain the silica-supported cobalt catalyst with the cobalt content of 1 wt%.
FIG. 1 shows N of the catalyst obtained in example 1 2 Adsorption and desorption isotherms and pore size distribution maps, the biomass silica-supported cobalt metal catalyst shows a combined isotherm of type I and type IV, indicating the presence of a microporous and mesoporous structure. The BET specific surface area of the catalyst was calculated to be 49.2m 2 (ii) in terms of/g. As can be seen from the pore size distribution diagram, the main pore size distribution in the catalyst is around 4 nm. Such a mesoporous structure is advantageous
FIG. 2 is an X-ray diffraction pattern (XRD) of example 1. As can be seen from the diffractogram, the catalyst sample showed a large diffraction peak at only 2 θ =21 ° which was attributed to the amorphous silica in the catalyst, and it can be shown that the cobalt species in the catalyst were uniformly dispersed on the support and thus were difficult to be detected.
FIG. 3 is a UV-vis-diffuse reflectance spectrum (UV-vis-DRS) of the catalyst prepared in example 1. The catalyst showed three absorption peaks at 520, 588 and 650nm, with the absorption peak at 520nm being attributed to tetrahedrally coordinated Co 2+ The 4T1g → 4T1g (P) transition, the two absorption peaks at 588 and 650nm are characteristic peaks of surface cobalt silicate. Co is not shown in the figure 3 O 4 Characteristic peak of (2), indicating the absence of Co in the catalyst 3 O 4 Is present.
FIG. 4 shows H of the catalyst obtained in example 1 2 Temperature programmed reduction curves, from which it can be seen that the catalyst presents three distinct reduction peaks at 590 ℃, 730 ℃ and 840 ℃, respectively related to the presence of hydrated cobalt silicate, surface cobalt silicate and bulk cobalt silicate that is difficult to reduce, these Co species being formed due to the reaction of Co complexes with the silicon hydroxyls on the surface of the support, or the strong interaction of Co species with the support due to the high dispersion of Co species on the surface of the catalyst. However, the catalyst does not show a reduction peak below 500 ℃, which indicates that Co is not formed in the preparation process of the catalyst 3 O 4 。
Example 2
The biomass silica-supported cobalt catalyst with 1wt% of cobalt content prepared in example 1 was used for the synthesis of single-walled carbon nanotubes by chemical vapor deposition: 200mg of the catalyst was packed in a porcelain boat and placed in the middle of a tube furnace, and then the catalyst was reduced from room temperature to 700 ℃ under pure hydrogen (150 sccm) at a temperature rise rate of 10 ℃/min. Then, the temperature is continuously increased to 900 ℃ at the temperature increase rate of 10 ℃/min in the argon atmosphere, absolute ethyl alcohol (60 ℃) is continuously blown into the reaction system by argon of 500sccm for 30min, and then the sample is naturally cooled to the room temperature in the argon atmosphere to obtain the single-walled carbon nanotube sample.
Example 3
The specific procedure of using the biomass silica-supported cobalt catalyst having a cobalt content of 1wt%, prepared in example 1, in the synthesis of single-walled carbon nanotubes by chemical vapor deposition method was as described in example 2, except that the catalyst was further heated to 950 ℃ at a heating rate of 10 ℃/min in an argon atmosphere.
Example 4
The specific procedure of using the biomass silica-supported cobalt catalyst having a cobalt content of 1wt%, prepared in example 1, in the synthesis of single-walled carbon nanotubes by chemical vapor deposition method was as described in example 2, except that the catalyst was further heated to 1000 ℃ at a heating rate of 10 ℃/min in an argon atmosphere.
Fig. 5 is a Raman spectrum (Raman) chart of the single-walled carbon nanotube prepared in example 3. It can be seen that the spectra of the carbon nanotube samples synthesized at 950 ℃ have strong radial respiration vibration mode (RBM) and tangential vibration mode (G peak) at different excitation wavelengths (532, 633 and 785 nm), while the defect vibration mode (D peak) is weaker, indicating that high-quality single-walled carbon nanotubes are synthesized. The RBM peak position is utilized to carry out preliminary analysis on the pipe diameter of the single-walled carbon nanotube, and the selected calculation formula is as follows:
ωRBM＝(223.5cm -1 /d t )+12.5cm -1
wherein, ω RBM and d t The peak frequency of RBM and the tube diameter of single-walled carbon nanotube. Therefore, the distance is between 135 and 197cm -1 The RBM peak in the range corresponds to the single-walled carbon nanotube with the tube diameter range of 1.21-1.82 nm. With major RBM peaks at 186, 160 and 145cm -1 It shows that the sample synthesized at 950 deg.c mainly contains single-wall carbon nanotube with tube diameters of 1.29, 1.52 and 1.69 nm. Meanwhile, the RBM peaks of the single-wall carbon nanotube sample under the three excitation wavelengths are fewer, which indicates that the tube diameter distribution is narrower.
FIG. 6 is an ultraviolet-visible-near infrared (Uv-Vis-NIR) spectrum of the single-walled carbon nanotubes prepared in example 3. According to S 11 And S 22 And analyzing the chiral structure of the single-walled carbon nanotube at the peak position of the absorption peak. As shown in fig. 6, at S 22 In the area, the main adsorption peaks of the single-walled carbon nanotube are at 810 and 869nm, and are respectively assigned to the (9,8) carbon tube with the particle size of 1.17nm and the (10,9) carbon tube with the particle size of 1.24 nm. Accordingly, at S 11 In the region, the strongest absorption peaks are from (9,8) and (10,9) carbon tubes at 1378 and 1422nm, indicating that under this temperature condition, single-wall carbon nanotubes with a tube diameter of 1.2nm were synthesized.
It should be noted that the single-walled carbon nanotubes with a diameter of greater than 2nm exceed the characteristic ranges of raman and absorption spectra and cannot be detected by spectroscopic techniques, so transmission electron microscopy is often used to detect large-diameter carbon nanotubes.
Fig. 7 is a Transmission Electron Microscope (TEM) image of the single-walled carbon nanotubes prepared in example 3, in which the generation of the bundle-like single-walled carbon nanotubes was observed and the active metal particles of the catalyst were uniformly distributed on the surface of the support. In addition, the existence of a plurality of independent single-walled carbon nanotubes with large tube diameter can be observed from the graph, and the maximum tube diameter is 3.8nm.
FIG. 8 is the diameter distribution diagram of the single-walled carbon nanotubes obtained by TEM statistics of the samples prepared in example 3, and the results of statistical analysis on about 100 single-walled carbon nanotubes selected from the samples grown at 950 ℃ indicate that the average diameter of the single-walled carbon nanotube sample synthesized under the conditions is 2.3nm. Also, in the samples grown under this condition, 70.7% of the single-walled carbon nanotubes were observed to have a tube diameter of more than 2nm.
FIG. 9 is a Scanning Electron Microscope (SEM) image of the single-walled carbon nanotubes prepared in example 3, wherein the single-walled carbon nanotubes are distributed on the surface of the catalyst, combined in a cluster form and intertwined with each other. And, its length can be up to several micrometers. Indicating that higher yields of single-walled carbon nanotubes were synthesized under this growth condition.
According to the analysis of the characterization results of the examples 1 and 3, the invention successfully develops a method for synthesizing the large-diameter single-walled carbon nanotube by using the supported catalyst based on the silicon-containing biomass, and determines the preparation method of the catalyst and the synthesis conditions of the large-diameter single-walled carbon nanotube, namely, a biomass silicon-based catalyst with a large number of pores less than 4nm is prepared, and when the cobalt content in the catalyst is 1wt%, the reduction temperature of the catalyst is 700 ℃, and the growth temperature is 950 ℃, the catalyst is used for the large-diameter single-walled carbon nanotube (d) t > 2 nm) has good selectivity.
The above-mentioned examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Many other variations will be apparent to those skilled in the art in light of the above teachings. Here, too, all the implementation methods cannot be described. Thus, obvious variations or modifications of the above-described embodiments are within the scope of the present invention.
Claims (8)
1. The preparation method of the biomass silicon-based catalyst for synthesizing the large-diameter single-walled carbon nanotube is characterized by comprising the following steps of:
(1) Preparation of a biomass silica carrier: pretreating the biomass material to remove surface impurities and soluble metal salts; burning at high temperature to obtain biomass silicon dioxide; the high specific surface area silicon dioxide with proper size is obtained by ball milling treatment.
(2) Preparation of the biomass silicon-based catalyst: dissolving a certain mass of metal salt by using a certain volume of solvent, slowly dripping the metal salt solution into the silicon dioxide carrier obtained in the step (1), stirring for a period of time at normal temperature in a water bath, then heating to 60 ℃, continuously stirring until no excess solvent exists, placing the mixture in an oven for drying overnight at 60 ℃, finally grinding and roasting the dried catalyst to obtain the biomass silicon-based catalyst.
2. The preparation method according to claim 1, wherein the biomass raw material used in the step (1) is one or a mixture of several of rice hull, straw, corn stalk, sorghum stalk, oat, barley, rice chaff or sorghum husk; the solvent used for pretreatment is sulfuric acid, hydrochloric acid, nitric acid or ionic liquid, the pretreatment time is 30min-2h, and the pretreatment temperature is 20-60 ℃; the burning temperature is 300-800 ℃, and the burning time is 3-12h; the ball milling speed is 300-600r/min, and the ball milling time is 2-72h.
3. The method according to claim 1-2, wherein the transition metal salt in step (2) is selected from one or more of metal salts containing iron, cobalt, nickel, copper, molybdenum, vanadium, etc. Preferably, the cobalt salts are selected from cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt acetate and cobalt oxalate.
4. The method of preparing a catalyst according to any one of claims 1 to 3, wherein the metal loading of the catalyst in step (2) is from 1wt% to 10wt%; the metal salt solvent is ethanol, methanol, or dichloromethane; the roasting temperature of the catalyst is 100-800 ℃, the roasting time is 3h, and the heating rate is 2 ℃/min.
5. Preparation of biomass silicon-based catalyst for synthesizing large-diameter single-walled carbon nanotubes as claimed in claim 1 to 4, which is prepared by the preparation method as claimed in any one of claims 1 to 4.
6. The method is used for synthesizing the large-diameter single-walled carbon nanotubes by the biomass silicon-based catalyst in the chemical vapor deposition method, and is characterized by comprising the following steps of: the catalyst of claim 5, 200mg of which is filled in a porcelain boat and placed in the middle of a tube furnace, and the temperature is raised from room temperature to a reduction temperature in a hydrogen atmosphere; and then heating to the reaction temperature in an inert atmosphere, immediately carrying carbon source ethanol into the tubular furnace from the water bath by using inert gas when the temperature reaches the reaction temperature, immediately stopping introducing the ethanol after the reaction is finished, and naturally cooling the reaction system to the room temperature in the inert atmosphere to obtain the large-diameter single-walled carbon nanotube sample.
7. The method as claimed in claim 6, wherein the reduction temperature during the synthesis process by chemical vapor deposition is 500-900 ℃, the growth temperature is 900-1000 ℃, the growth time is 3-60min, the inert gases used are argon and nitrogen, the flow rate of the inert gas is 30-100sccm, the flow rate of the reducing gas hydrogen used is 100-200sccm, and the flow rate of the ethanol gas is 300-700sccm.
8. The method as claimed in claims 6 and 7, wherein the biomass silicon-based catalyst of claim 5 can selectively prepare single-walled carbon nanotubes with a tube diameter of more than 2nm and narrow tube diameter distribution when the growth temperature is 950 ℃.
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