CN110040718B - Preparation method of thiacalixarene-based multi-walled carbon nanotube derived from 16 nuclear molecular cluster - Google Patents

Abstract

The invention discloses a method for preparing multi-walled carbon nanotubes derived from thiacalixarene-based 16-nuclear molecular clusters. The technical scheme includes the following steps: (1) preparation and spin coating of M16; Aromatics _H4BTC4A (0.1 mmol), NiCl2.6H2O ₍ 0.4 mmol), Dy(OAc) _3.6H2O (0.3 mmol) and _{Na2CO3 (} 0.2 mmol ₎ in DMA _{/ CH3CN} /Et Mixed in ₃ N, then transferred to the reaction kettle for 6 days at 130 °C, then slowly cooled to room temperature, and named M16: Take macromolecular cluster M16 in a test tube, add 10 mL of _CHCl3 to dissolve, and spin-coat It is dispersed on a quartz substrate and used as a catalyst precursor. (2) Preparation of carbon nanotubes by chemical vapor deposition. The material required by the invention is cheap, the preparation process is simple, the preparation period is short, and the reaction conditions are simple. operability and practicability, among which it has potential application value and strong practicability in the fields of electrocatalytic performance.

Description

A kind of preparation method of multi-walled carbon nanotubes derived from thiacalixarene 16-nuclear molecular clusters

technical field

The invention belongs to the technical field of micro-nano material synthesis, and in particular relates to a preparation method of multi-walled carbon nanotubes derived from thiacalixarene 16-core molecular clusters.

Background technique

Carbon nanotubes, as one-dimensional nanomaterials, are light in weight, have perfectly connected hexagonal structures, and possess many unusual mechanical, electrical and chemical properties. In recent years, with the in-depth research of carbon nanotubes and nanomaterials, their broad application prospects have also been continuously shown. Carbon nanotubes can be regarded as rolled graphene sheets, so according to the number of graphene sheets, they can be divided into: single-walled carbon nanotubes (or single-walled carbon nanotubes, Single-walled Carbon nanotubes, SWCNTs) and Multi-walled carbon nanotubes (or multi-walled carbon nanotubes, Multi-walled Carbon nanotubes, MWCNTs). Carbon nanotubes have good mechanical properties. The hardness of carbon nanotubes is comparable to that of diamond, but they have good flexibility and can be stretched. Furthermore, carbon nanotubes have the highest melting point of any known material.

Commonly used preparation methods of carbon nanotubes are: arc discharge method, laser ablation method, chemical vapor deposition method (hydrocarbon gas pyrolysis method), solid phase pyrolysis method, glow discharge method, gas combustion method and polymerization synthesis. law, etc. Among them, the chemical vapor deposition method has become an economical method due to its advantages of low preparation temperature, low cost, and large-area preparation, and thus has been widely studied. However, the method for preparing carbon materials still needs to be developed, and it is still very challenging to use simple, reproducible, and low-cost synthetic methods to prepare carbon materials.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a method for preparing multi-walled carbon nanotubes derived from thiacalixarene 16-nuclear molecular clusters in order to overcome the shortcomings and deficiencies of the prior art. The method requires low cost materials, simple preparation process, short preparation period, simple reaction conditions, regular morphology of the prepared product, large specific surface area, strong morphology controllability, good stability and repeatability, and has strong operability and practicability, among which it has potential application value and strong practicability in the fields of electrocatalytic performance.

In order to achieve the above object, the technical scheme of the present invention is

(1) Preparation and spin coating of M16

Consists of 0.1 mmol of tert-butylthiacalixarene H ₄ BTC4A, 0.4 mmol of NiCl ₂ 6H ₂ O, 0.3 mmol of Dy(OAc) ₃ 6H ₂ O and 0.2 mmol of Na ₂ CO ₃ in volumes of 6 , 3, and 0.5 mL of DMA/CH ₃ CN/Et ₃ N, and then transferred to the reaction kettle to react at 130°C for 6 days, and then slowly cooled to room temperature to obtain green bulk crystals, which were named M16. Take 1 mg of macromolecular cluster M16 in a test tube, add 10 ml of CHCl ₃ to dissolve, take a drop of the prepared solution and disperse it on a quartz substrate by spin coating as a catalyst precursor;

(2) Obtaining carbon nanotubes M16-CNT by chemical vapor deposition

The growth of carbon nanotubes is carried out in a furnace with a 1-inch tube, and the quartz substrate with the M16 substance dispersed in step (1) is placed on a quartz boat and placed in the tube, and placed in an argon gas of 300 standard cubic centimeters per minute. The chemical vapor deposition tube furnace was calcined in a medium atmosphere, and the furnace temperature was raised to 800 °C at a heating rate of 10 °C/min. After purging the system with argon, a hydrogen flow of 100 scc/min and ethylene of 50 scc/min were introduced to make the system. The carbon nanotubes were grown at 800° C. for 30 minutes, and the resulting carbon nanotubes were densely distributed on the surface of the quartz substrate.

It is further set that the molecular weight of M16 in the step (1) is 1357.

A further setting is that the diameter of the resulting carbon nanotubes is about 20 nm.

The further arrangement is that the obtained carbon nanotubes are in the shape of bamboo knots, and the tips of each nanotube are attached with M16 catalyst particles.

The further setting is that the carbon nanotubes have the characteristics of micropores and mesopores, and their specific surface area is 66.2m ² g ^-1 by BET test.

The further setting is that the lattice fringe spacing of the obtained carbon nanotubes is 0.31 nm, which corresponds to the (002) crystal plane of the C atom.

The invention utilizes a preparation method of multi-walled carbon nanotubes derived from thiacalixarene 16-nuclear molecular clusters. The material required by the invention is cheap, the preparation process is simple, the preparation period is short, and the reaction conditions are simple. operability and practicability, among which it has potential application value and strong practicability in the fields of electrocatalytic performance.

Description of drawings

In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that are used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only These are some embodiments of the present invention, and for those of ordinary skill in the art, obtaining other drawings according to these drawings still belongs to the scope of the present invention without any creative effort.

Fig. 1 is the crystal structure diagram of macromolecular cluster M16 synthesized by solvothermal method of the present invention;

Fig. 2 is the gel permeation chromatogram of M16;

Fig. 3 is the powder X-ray diffraction (PXRD) pattern of M16;

Fig. 4 is the thermogravimetric analysis (TGA) figure of M16 under argon atmosphere;

Figure 5 is a scanning electron microscope (SEM) image of M16-CNT synthesized by chemical vapor deposition method; wherein, the scales corresponding to the SEM image are 20 μm and 5 μm, respectively;

Figure 6 is a transmission electron microscope (TEM) image of M16-CNT synthesized by chemical vapor deposition method; wherein, the scales corresponding to the TEM image are 200 nm and 10 nm, respectively;

7 is a Raman curve diagram of M16-CNT obtained by chemical vapor deposition (CVD);

Figure 8 is the _N2 adsorption-desorption curve of M16-CNT obtained by chemical vapor deposition (CVD).

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings.

The invention discloses a preparation method of multi-walled carbon nanotubes derived from thiacalixarene 16-core molecular clusters. The method uses the macromolecular cluster M16 as a raw material, and adopts chemical vapor deposition (CVD) to obtain the multi-walled carbon nanotubes M16-CNT; in other words, the present invention provides a novel preparation method of the multi-walled carbon nanotubes. The preparation method of the multi-walled carbon nanotube M16-CNT according to the present invention comprises the following steps:

(1) Preparation and spin coating of M16. From tert _- butylthiacalixarene _H4BTC4A (0.1 mmol, 72 mg), NiCl2.6H2O (0.4 mmol, 95 _mg ), Dy(OAc) _3.6H2O (0.3 mmol, 132 _mg ) and _{Na2CO 3} (0.2 mmol, 21 mg) was mixed in DMA/CH ₃ CN/Et ₃ N (6/3/0.5 mL), then transferred to the reaction vessel and reacted at 130°C for 6 days, then slowly cooled to room temperature to obtain green Bulk crystal, named M16: [Na ₂ Ni ^II ₁₂ Ln ^III ₂ (BTC4A) ₃ (μ ₇ -CO ₃ ) ₃ (μ ₃ -OH) ₄ (μ ₃ -Cl) ₂ -(OAc) ₆ (dma) ₄ ] 2OAc 0.5dma 3MeCN 8DMA (Ln=Dy; H ₄ BTC4A=p-tert-butylthiacalix[4]arene; dma=dimethylamine and DMA=N,N'-dimethylacetamide). Take 1 mg of macromolecular cluster M16 in a test tube, add 10 mL of CHCl ₃ to dissolve, and take a drop of the prepared solution and disperse it on a quartz substrate by spin coating as a catalyst precursor.

(2) Carbon nanotube growth was performed in a furnace with a 1-inch tube. Quartz substrates with well-dispersed M16 species were placed on a quartz boat into tubes and calcined in a chemical vapor deposition (CVD) tube furnace under an argon atmosphere of 300 standard cubic centimeters per minute (scc/min). , the furnace temperature was raised to 800°C at a heating rate of 10°C/min. After purging the system with argon, a flow of hydrogen (100 scc/min) and ethylene (50 scc/min) were introduced, and carbon nanotubes were grown at 800° C. for 30 minutes. The resulting M16-CNTs were naturally cooled to room temperature. The obtained carbon nanotubes M16-CNTs were characterized by FE-SEM, TEM, EDX and PXRD. SEM images show the formation of densely distributed carbon nanotubes on the surface of the quartz substrate after calcination. The diameter of the nanotubes is about 10 nm. It was confirmed by TEM that the multi-walled carbon nanotubes were bamboo-like, and the tips of each nanotube were attached with nano-catalytic particles. The lattice fringe spacing is 0.31 nm, which corresponds to the (002) plane of C.

Fig. 1 is the crystal structure diagram of the macromolecular cluster M16 synthesized by the solvothermal method of the present invention. It can be seen from the figure that it is a 16-nucleated shuttlecock-shaped molecular cluster, which is composed of two sodium cations, two lanthanides, respectively. Cation, twelve nickel ions and three tert-butyl thiacalixarenes;

Figure 2 is a gel permeation chromatogram of M16, from which it can be seen that the GPC test results are number average molecular weight Mn=1152, weight average molecular weight Mw=1357, and PDI (polydispersity)=Mw/Mn=1.17.

Figure 3 is a powder X-ray diffraction (PXRD) pattern of M16, from which it can be seen that the obtained M16 is in good comparison with the simulated data.

Figure 4 is a thermogravimetric analysis (TGA) diagram of M16 in an argon atmosphere. It can be seen from the figure that the obtained M16 has begun to lose weight at a lower temperature in an argon atmosphere.

Figure 5 is a scanning electron microscope (SEM) image of M16-CNT synthesized by chemical vapor deposition. It can be seen from the figure that densely distributed multi-walled carbon nanotubes are formed on the surface of the quartz substrate after calcination. The diameter of the nanotubes is about 10 nm.

Figure 6 is a transmission electron microscope (TEM) image of M16-CNT synthesized by chemical vapor deposition. It can be seen from the figure that the obtained multi-walled carbon nanotubes are in the shape of bamboo knots, and the tips of each nanotube are attached with nano catalytic particles . The lattice fringe spacing is 0.31 nm, which corresponds to the (002) plane of C.

Figure 7 is a Raman curve diagram of M16-CNT obtained by chemical vapor deposition (CVD). It can be seen from the figure that: D peak/G peak = 1.2, the degree of graphitization is not high, and it is mainly amorphous carbon.

Figure ₈ shows the N adsorption-desorption curve of M16-CNT obtained by chemical vapor deposition (CVD). It can be seen from the figure that it has the characteristics of mesopores and macropores, and its specific surface area is ^66.2m2g by BET test ^-1 .

The above disclosures are only preferred embodiments of the present invention, and of course, the scope of the rights of the present invention cannot be limited by this. Therefore, equivalent changes made according to the claims of the present invention are still within the scope of the present invention.

Claims (6)

1. A preparation method of a multi-walled carbon nanotube derived from thiacalixarene-based 16-nuclear molecular cluster is characterized by comprising the following steps:

(1) preparation and spin coating of M16

From 0.1mmol of tert-butylthiacalixarene H₄BTC4A, 0.4mmol of NiCl₂·6H₂O, 0.3mmol of Dy (OAc)₃·6H₂O and 0.2mmol of Na₂CO₃In DMA/CH with volumes of 6, 3 and 0.5mL respectively₃CN/ Et₃Mixing in N, transferring to a reaction kettle, reacting at 130 deg.C for 6 days, and reactingSlowly cooling to room temperature to obtain green block crystal, which is named as M16, taking 1mg of macromolecular cluster M16 in a test tube, and adding 10ml of CHCl₃Dissolving, and taking a drop of prepared solution to be dispersed on a quartz substrate by a spin coating method to be used as a catalyst precursor;

(2) obtaining the carbon nano tube M16-CNT by using a chemical vapor deposition method

And (2) growing the carbon nano tubes in a furnace with a 1-inch tube, placing the quartz substrate dispersed with the M16 substance obtained in the step (1) on a quartz boat, placing the quartz boat in the tube, calcining the quartz substrate in a chemical vapor deposition tube furnace in an argon atmosphere of 300 standard cubic centimeters per minute, raising the temperature of the furnace to 800 ℃ at a heating rate of 10 ℃/min, purging the system with argon, introducing a hydrogen flow of 100scc/min and ethylene of 50scc/min, and growing the carbon nano tubes at 800 ℃ for 30 minutes to obtain the carbon nano tubes densely distributed on the surface of the quartz substrate.

2. The method of preparing the thiacalixarene-based 16-nuclear molecular cluster-derived multi-walled carbon nanotubes as claimed in claim 1, wherein the method comprises the steps of: the weight average molecular weight of M16 in step (1) was 1357.

3. The method of claim 1 for preparing thiacalixarene-based 16-core molecular cluster derivatized multi-walled carbon nanotubes, wherein: the diameter of the carbon nanotubes produced was about 20 nm.

4. The method of preparing the thiacalixarene-based 16-nuclear molecular cluster-derived multi-walled carbon nanotubes as claimed in claim 1, wherein the method comprises the steps of: the obtained carbon nano-tubes are bamboo-shaped, and M16 catalyst particles are attached to the tip of each nano-tube.

5. The method of claim 1 for preparing thiacalixarene-based 16-core molecular cluster derivatized multi-walled carbon nanotubes, wherein: the obtained carbon nano tube has the characteristics of micropores and mesopores, and the specific surface area is 66.2m through a BET test² g^-1。

6. The method of preparing the thiacalixarene-based 16-nuclear molecular cluster-derived multi-walled carbon nanotubes as claimed in claim 1, wherein the method comprises the steps of: the lattice fringe spacing of the obtained carbon nanotube was 0.31nm, corresponding to the (002) crystal face of C.

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