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CN-122010099-A - One-dimensional hollow carbon nanomaterial constructed based on spherical holes and preparation method and application thereof

CN122010099ACN 122010099 ACN122010099 ACN 122010099ACN-122010099-A

Abstract

The invention discloses a one-dimensional hollow carbon nano material based on spherical hole construction, a preparation method and application thereof, belonging to the technical field of mesoporous materials, wherein the method adopts a magnetic field to induce Fe 3 O 4 nanospheres to assemble into a chain structure, and after silicon dioxide is coated, the PS-PEO-PVP segmented copolymer micelle is utilized to carry out super-assembly on the surface, and then the one-dimensional hollow carbon nanomaterial which is provided with mutually communicated spherical macropores and orderly spherical mesopores uniformly distributed on the inner wall is obtained through dopamine cladding, high-temperature carbonization and template etching. The material has the length of 600nm-1um, good dispersibility and adjustable structure. Experiments show that the catalyst has higher power generation voltage and excellent cycle stability than commercial carbon nanotubes in evaporation direct current power generation, and has wide application prospect in the fields of high-efficiency electrodes, catalyst carriers and the like.

Inventors

  • ZHAO YUJUAN
  • KONG MENG
  • ZHAO ZAIWANG
  • DING YIFAN
  • WANG TIAN
  • ZHANG QINGNUAN
  • WEI BO
  • ZHAO DONGYUAN

Assignees

  • 内蒙古大学

Dates

Publication Date
20260512
Application Date
20260413

Claims (9)

  1. 1. The preparation method of the one-dimensional hollow carbon nanomaterial constructed based on spherical holes is characterized by comprising the following steps of: Synthesizing Fe 3 O 4 nanospheres by adopting a solvothermal method, dispersing the nanospheres in a mixed solvent, arranging the Fe 3 O 4 nanospheres into a chain structure under the action of an external magnetic field, then adding a silicon source, coating a silicon dioxide shell layer on the surface of the chain structure of the Fe 3 O 4 nanospheres, wherein the mass ratio of the silicon source to the Fe 3 O 4 nanospheres is 1:20, magnetically separating and washing to obtain a Fe 3 O 4 @SiO 2 core-shell nanosphere, and dissolving for later use; Step two, dissolving a polystyrene-polytetravinyl pyridine-polyethylene oxide triblock copolymer in absolute ethyl alcohol, stirring to dissolve the polystyrene-polytetravinyl pyridine-polyethylene oxide triblock copolymer, placing the mixture in an oven, heating the mixture at 70-100 ℃ for 3-5 hours to obtain a PS-PVP-PEO micelle solution, mixing the PS-PVP-PEO micelle solution with the Fe 3 O 4 @SiO 2 core-shell nano chains obtained in the step one, stirring the mixture at room temperature to ensure that the PS-PVP-PEO micelle is super-assembled on the surface of the Fe 3 O 4 @SiO 2 core-shell nano chain, wherein the volume ratio of the used micelle to the Fe 3 O 4 @SiO 2 core-shell nano chains is 5:1, and after the reaction is finished, collecting a product through magnetic separation and washing the product with water and ethanol to obtain Fe 3 O 4 @SiO 2 @micolle; Dispersing the product obtained in the step II in water, dropwise adding 6-7 mL of 0.01mol/L tris (hydroxymethyl) aminomethane solution, regulating the pH value to 8.5, adding dopamine hydrochloride for coating to form a dopamine coating layer, enabling the mass ratio of the dopamine hydrochloride to the Fe 3 O 4 @SiO 2 core-shell nano chains to be 10:1, magnetically separating, washing and drying to obtain Fe 3 O 4 @SiO 2 @PDA nano fibers, placing the product in a tube furnace, performing temperature programming treatment under a nitrogen atmosphere, then treating the product by using an etchant to remove Fe 3 O 4 cores and SiO 2 shells, and finally washing and drying to obtain the one-dimensional hollow carbon nano material.
  2. 2. The preparation method of the one-dimensional hollow carbon nanomaterial constructed based on spherical pores as claimed in claim 1, wherein in the first step, the Fe 3 O 4 nanospheres are prepared by adding 4-6g of ferric trichloride hexahydrate, 0.5-1g of sodium citrate and 5-9g of anhydrous sodium acetate into 30ml of ethylene glycol for dissolution, placing the mixture in an oven after full dissolution, and reacting at 180-200 ℃ for 5-10 hours to obtain the Fe 3 O 4 nanospheres, wherein the mixed solvent consists of water, ethanol and ammonia water.
  3. 3. The method for preparing the one-dimensional hollow carbon nanomaterial constructed based on spherical pores as claimed in claim 1, wherein in the first step, the diameter of the Fe 3 O 4 nanospheres is 100-300nm, and the silicon source is selected from one or more of tetraethyl orthosilicate, 1, 2-bis (triethoxysilyl) ethane, methyl orthosilicate, DMDMS, sodium silicate, methyltriethoxysilane and phenyltrimethoxysilane.
  4. 4. The method for preparing the one-dimensional hollow carbon nanomaterial constructed based on spherical pores as claimed in claim 1, wherein in the second step, the mixing volume ratio of the PS-PVP-PEO micelle solution to the Fe 3 O 4 @SiO 2 core-shell nano-chain is 5:1.
  5. 5. The method for preparing a one-dimensional hollow carbon nanomaterial based on spherical pore construction as claimed in claim 1, wherein in the second step, the concentration of the polystyrene-polytetravinylpyridine-polyethylene oxide triblock copolymer in the solvent is 0.2-20mg/mL.
  6. 6. The method for preparing a one-dimensional hollow carbon nanomaterial constructed based on spherical pores as claimed in claim 1, wherein in the second step, the stirring speed is 60-600rpm/min, and the reaction time is 3-15h.
  7. 7. The preparation method of the one-dimensional hollow carbon nanomaterial constructed based on spherical pores, as claimed in claim 1, is characterized in that in the third step, the temperature programming treatment is carried out by heating to 300-400 ℃ at 1-5 ℃ per min and preserving heat for 1-3 hours, then heating to 700-900 ℃ at 2-10 ℃ per min and preserving heat for 1-3 hours, and the etchant is hydrofluoric acid aqueous solution.
  8. 8. The one-dimensional hollow carbon nanomaterial constructed based on spherical pores is characterized in that the one-dimensional hollow carbon nanomaterial is prepared by the method of any one of claims 1-7, the one-dimensional hollow carbon nanomaterial is provided with mutually communicated spherical macropores, a layer of single-layer spherical mesopores are uniformly arranged on the inner wall of each spherical macropore, the pore size of each spherical macropore is 220-350nm, and the pore size of each spherical mesopore is 20-30nm.
  9. 9. The application of the one-dimensional hollow carbon nanomaterial constructed based on spherical pores in high-performance evaporation direct current power generation according to claim 8.

Description

One-dimensional hollow carbon nanomaterial constructed based on spherical holes and preparation method and application thereof Technical Field The invention belongs to the technical field of mesoporous materials, and particularly relates to a one-dimensional hollow carbon nanomaterial constructed based on spherical pores, a preparation method and application thereof. Background One-dimensional nanomaterials (e.g., nanowires, nanorods, nanotubes) exhibit unique advantages in terms of electron transport, mechanical strength, and as a self-supporting substrate due to their anisotropic morphology. The carbon nano tube is used as a typical one-dimensional hollow carbon nano material, has obvious structural advantages, and firstly, the hollow structure can ensure that the active site has sufficient contact area with the solution, can store more active substances and relieves structural stress in the chemical reaction process. Secondly, the nanoscale structural unit can shorten the diffusion path of electrons/ions, and the reaction kinetics and the utilization rate of active substances are improved. Finally, the one-dimensional structure facilitates electron transport. Based on the structural advantages, the one-dimensional hollow carbon nano structure is paid attention to in the fields of catalysis, energy sources, biomedicine and the like. The super-structure mesoporous material is a material with a multilevel ordered mesoporous structure (2-50 nm), and the pore canal arrangement, the component distribution and the macroscopic morphology of the super-structure mesoporous material can be accurately regulated and controlled. Compared with the traditional mesoporous materials (such as MCM-41, SBA-15 and other uniform pore structures), the super-structure mesoporous materials form a more complex topological structure through primitive assembly (such as nano particles, micelles, block copolymers and the like), and form unique advantages. However, how to organically combine the super-structured mesoporous with the one-dimensional hollow carbon material remains a challenge. Common methods for synthesizing the one-dimensional hollow mesoporous nano material mainly comprise a soft and hard template method based on templates, an electrostatic spinning method using a large instrument and a sacrificial template method based on a nano-scale Kendall effect and an ion exchange reaction. However, most samples prepared using these methods are limited by small pore size or irregular porosity, resulting in a loading of guest material in the pores and mass/ion transport efficiency limited by their pore size and structure. Therefore, a novel method for simply, conveniently and controllably preparing the carbon nanomaterial with spherical mesopores which are orderly arranged through one-dimensional hollow channels and inner walls is developed, and has important significance for promoting the application of the carbon nanomaterial in the fields of high-efficiency electrodes, catalyst carriers and the like. Disclosure of Invention Aiming at the defect that the prior art is difficult to simply prepare the carbon nanomaterial with one-dimensional hollow morphology and ordered multi-stage pore canal, the invention aims to provide the one-dimensional hollow carbon nanomaterial constructed based on spherical pores, and the preparation method and the application thereof, the method combines magnetic field induction assembly and block copolymer micelle domain-limited super assembly, the magnetic Fe 3O4 nanospheres are used as structural guide elements to construct a one-dimensional hollow skeleton and an internal through spherical macroporous (200-400 nm), meanwhile, PS-PVP-PEO micelles are utilized to perform super assembly on the inner wall of a pore canal and are converted into ordered spherical mesopores (20-50 nm), the width of the synthesized one-dimensional hollow carbon nanomaterial is about 250nm, the length is 600nm-1um, and the one-dimensional hollow carbon nanomaterial has good dispersibility and uniformity. The invention is realized by the following technical scheme: in a first aspect, the present invention provides a method for preparing a one-dimensional hollow carbon nanomaterial constructed based on spherical pores, comprising the steps of: Synthesizing Fe 3O4 nanospheres by adopting a solvothermal method, dispersing the obtained Fe 3O4 nanospheres in a mixed solvent consisting of water, ethanol and ammonia water, arranging the Fe 3O4 nanospheres into a chain structure under the action of an external magnetic field, then adding a silicon source, coating a silicon dioxide shell layer on the surface of the chain structure of the Fe 3O4 nanospheres, wherein the mass ratio of the silicon source to the Fe 3O4 nanospheres is 1:20, magnetically separating and washing to obtain Fe 3O4@SiO2 core-shell nanospheres, and dissolving the Fe 3O4@SiO2 core-shell nanospheres in 30mL absolute ethyl alcohol for later use; Dissolving 40mg of pol