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CN-122006691-A - Pore-diameter-controllable carbon material and preparation method and application thereof

CN122006691ACN 122006691 ACN122006691 ACN 122006691ACN-122006691-A

Abstract

The invention provides a carbon material with controllable pore diameter, a preparation method and application thereof. The preparation method comprises the steps of dissolving a rigid 'androstane' organic precursor in a dichloromethane solvent, adding a template agent, sequentially pre-coating, heating to carbonize, and removing the template agent to obtain the carbon material. The prepared carbon material supported Pd two-dimensional nano-sheet is prepared into a hydrodeoxygenation catalyst, and the hydrodeoxygenation catalyst is applied to the selective hydrogenolysis process of C-O bonds, has high activity, high selectivity and excellent cycle stability, the selectivity of alkane target products can reach 100%, the hydrogenolysis condition is mild, and the reactivity is more than or equal to 99.9%.

Inventors

  • WEI XUEMEI
  • Shen Runbu
  • SHEN HUALIANG
  • YU GUOQI
  • XIE MENGYU
  • WU YINHAO
  • HU KAI
  • XU HAONAN
  • Che Cilei

Assignees

  • 绍兴文理学院

Dates

Publication Date
20260512
Application Date
20260104

Claims (10)

  1. 1. A preparation method of a carbon material with controllable pore diameter is characterized by comprising the following steps: Dissolving a rigid organic precursor in a dichloromethane solvent, adding a template agent, sequentially pre-coating, performing temperature programming carbonization, and removing the template agent to obtain the carbon material; wherein the structural formula of the rigid organic precursor is shown as a formula I; Formula I.
  2. 2. The method for preparing a carbon material with controllable pore diameter as claimed in claim 1, wherein the template agent is SiO 2 , and the size of the SiO 2 template agent is 10-50 nm.
  3. 3. The method for preparing a carbon material with controllable pore diameter as claimed in claim 1, wherein the mass ratio of the rigid organic precursor to the template agent is 1:0.5-2.
  4. 4. The method for preparing the carbon material with the controllable pore diameter according to claim 1, wherein the pre-coating condition is that the solvent is dried by spin drying at 30 ℃ and finally vacuum drying at 70-80 ℃ after stirring for 10-60 min.
  5. 5. The method for preparing the carbon material with the controllable pore diameter according to claim 1, wherein the temperature programming carbonization condition is that the temperature is raised to 400-410 ℃ at a temperature rise rate of 2 ℃ per minute for 1-1.5 hours under an inert atmosphere, the temperature is continuously raised to 600-800 ℃ at a temperature rise rate of 5 ℃ per minute for 1-2 hours, and finally the carbon material is naturally cooled to room temperature.
  6. 6. The method for preparing the carbon material with controllable pore diameter according to claim 1, wherein the template removing agent comprises the steps of placing carbonized material in a sodium hydroxide solution, performing ultrasonic treatment at 50-60 ℃ for 6-8 hours, performing centrifugal separation, washing and vacuum drying to obtain the carbon material; Wherein the concentration of the sodium hydroxide solution is 5-7 mol/L.
  7. 7. A carbon material with controllable pore diameter obtained by the preparation method according to any one of claims 1 to 6, which is characterized in that the carbon material is in a shape of bath flower, and the specific surface area is 200-500 m 2 /g.
  8. 8. A hydrodeoxygenation catalyst, which is characterized by comprising a carrier and Pd two-dimensional nano-sheets supported on the surface of the carrier, wherein the carrier is selected from the carbon materials in claim 7, and the Pd two-dimensional nano-sheets expose (111) crystal faces.
  9. 9. The hydrodeoxygenation catalyst according to claim 9, wherein the Pd two-dimensional nano-sheet has a particle size of 3-5 nm and a thickness of 0.8-1.2 nm; The load of the Pd two-dimensional nano-sheets in the hydrodeoxygenation catalyst is 3-5%.
  10. 10. Use of the hydrodeoxygenation catalyst of claim 8 or 9 in the selective hydrogenolysis of C-O bonds.

Description

Pore-diameter-controllable carbon material and preparation method and application thereof Technical Field The invention relates to the technical field of catalytic materials, in particular to a carbon material with controllable pore diameter, a preparation method and application thereof. Background Selective Hydrodeoxygenation (HDO) of aromatic alcohols and their derivatives is a core catalytic process that cleaves c—o bonds and converts oxygen-containing functional groups directly into alkyl groups. The process not only synthesizes complex natural products, pharmaceutically active molecules and efficient ways of high value-added chemicals, but also, most importantly, converts renewable biomass platform molecules (such as lignin derivatives) into liquid hydrocarbon fuels or chemical raw materials with high efficiency. Therefore, the development of heterogeneous catalysts that are efficient, stable and selective during the conversion process is a central challenge in achieving their industrial application. Carbon materials play a critical role in HDO reactions due to their excellent chemical stability, controllable surface properties, and rich pore structures, as well as good metal dispersibility. The catalyst can be used as an ideal carrier of a high-performance catalyst, can also show intrinsic catalytic activity in certain reactions, and currently common carbon materials mainly comprise active carbon, nano-structure carbon (such as carbon nano-tubes, graphene and graphene oxide) and various biomass-derived carbon materials. However, the existing carbon materials still have the defects that (1) the pore size distribution of most carbon materials is wide and nonuniform, a large number of micropores and dead holes exist, the diffusion resistance of reactants and products is increased, the mass transfer efficiency is reduced, and the pore channels are easily blocked by carbon deposition or macromolecule byproducts to deactivate, 2, partial carbon material structures are easily collapsed or sintered under a high-temperature environment, so that the specific surface area and the porosity are obviously reduced, meanwhile, the surface acidic sites can promote the generation and deposition of coke to further accelerate the deactivation of the catalyst, and 3, the macroscopic morphology of the carbon materials and the lack of effective cooperative regulation means between the pore channel structures and microscopic surface chemical properties are provided. Thus limiting further increases in the selectivity and efficiency of the carbon material. Therefore, development of a novel carbon material which is highly ordered, uniform and adjustable in pore diameter and excellent in high stability is a problem to be solved. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a carbon material with controllable pore diameter, a preparation method and application thereof, and solves the problems in the prior art. In order to achieve the above purpose, the invention is realized by the following technical scheme: According to a first aspect of the present invention, there is provided a method for preparing a pore-size-controllable carbon material, comprising the steps of: Dissolving a rigid organic precursor in a dichloromethane solvent, adding a template agent, sequentially pre-coating, performing temperature programming carbonization, and removing the template agent to obtain the carbon material; wherein the structural formula of the rigid organic precursor is shown as a formula I; Formula I. Preferably, the template agent is selected from SiO 2 template agents, and the size of the SiO 2 template agent is 10-50 nm. Further preferably, the size of the SiO 2 template agent is 20-30 nm. Preferably, the mass ratio of the rigid organic precursor to the template agent is 1:0.5-2. Specifically, the mass ratio of the rigid organic precursor to the template agent is selected from any ratio of 1:0.5, 1:1, 1:1.5, 1:2 or a range value between any ratios. Preferably, the pre-coating condition is that the solvent is firstly stirred for 10-60 min, then dried at 30 ℃ in a spin mode, and finally dried at 70-80 ℃ in a vacuum mode. Preferably, the temperature programming carbonization condition is that in an inert atmosphere, the temperature is raised to 400-410 ℃ at a temperature raising rate of 2 ℃ per minute for 1-1.5 hours, then the temperature is continuously raised to 600-800 ℃ at a temperature raising rate of 5 ℃ per minute for 1-2 hours, and finally the temperature is naturally cooled to room temperature. Preferably, the template removing agent is prepared by placing carbonized materials in a sodium hydroxide solution, performing ultrasonic treatment at 50-60 ℃ for 6-8 hours, performing centrifugal separation, washing and vacuum drying to obtain the carbon materials; Wherein the concentration of the sodium hydroxide solution is 5-7 mol/L. According to a second aspect of the invention, a carbon material