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CN-121653749-B - Double-tooth ligand supported covalent organic framework hydrogen evolution catalyst and preparation method and application thereof

CN121653749BCN 121653749 BCN121653749 BCN 121653749BCN-121653749-B

Abstract

The invention discloses a covalent organic framework hydrogen evolution catalyst supported by a bidentate ligand, a preparation method and application thereof, wherein 1,3, 5-trimethyl phloroglucinol and o-phenylenediamine are added into an organic solvent I to be mixed uniformly, an acid catalyst is added for reaction after degassing, the obtained filter solid is washed and dried through the organic solvent II after the reaction is finished, the covalent organic framework is obtained, the filter solid and a metal salt are added into the organic solvent I to be mixed uniformly, the acid catalyst is added for reaction after degassing, the obtained filter solid is washed and dried through the organic solvent II after the reaction is finished, the obtained filter solid and the bidentate ligand are added into the organic solvent I to be mixed uniformly, the acid catalyst is added for reaction after degassing, and the obtained filter solid is washed and dried through the organic solvent II after the reaction is finished, thus obtaining the covalent organic framework hydrogen evolution catalyst supported by the bidentate ligand to be prepared. The preparation method is simple, short in synthesis period, low in preparation cost and very friendly to the environment.

Inventors

  • CUI GUOKAI
  • JIANG TAO
  • ZHANG RUINA
  • ZHOU YING
  • LU HANFENG

Assignees

  • 浙江工业大学

Dates

Publication Date
20260505
Application Date
20260209

Claims (10)

  1. 1. The preparation method of the covalent organic framework hydrogen evolution catalyst supported by the bidentate ligand is characterized by comprising the following steps of: 1) The preparation of the covalent organic framework comprises the steps of adding 1,3, 5-trimethyl phloroglucinol, o-phenylenediamine and an acid catalyst into an organic solvent I, uniformly mixing, then degassing, carrying out reaction after degassing, filtering the reacted material after the reaction is finished, washing the obtained filter solid by an organic solvent II, and drying to obtain the covalent organic framework to be prepared; 2) Adding the covalent organic framework, metal salt and acid catalyst obtained in the step 1) into an organic solvent I, uniformly mixing, then degassing, carrying out a reaction after degassing, filtering the reacted material after the reaction is finished, washing the obtained filter solid by an organic solvent II, and drying to obtain the metal-doped covalent organic framework to be prepared; 3) Adding the metal doped covalent organic framework, the bidentate ligand and the acid catalyst obtained in the step 2) into an organic solvent I, uniformly mixing, then degassing, carrying out reaction after degassing, filtering the reacted material after the reaction is finished, washing the obtained filter solid by an organic solvent II, and drying to obtain the covalent organic framework hydrogen evolution catalyst supported by the bidentate ligand to be prepared; the metal salt is cobalt acetate, and the bidentate ligand is triethylene diamine.
  2. 2. The preparation method of the bidentate ligand supported covalent organic framework hydrogen evolution catalyst is characterized in that the mass ratio of 1,3, 5-trimethyl phloroglucinol to o-phenylenediamine in the step 1) is 1:1-3, the mass ratio of 1,3, 5-trimethyl phloroglucinol to acid catalyst is 1:2-4, the reaction temperature in the step 1) is 100-150 ℃, and the reaction time is 48-96 h.
  3. 3. The preparation method of the bidentate ligand supported covalent organic framework hydrogen evolution catalyst is characterized in that the mass ratio of the covalent organic framework to the metal salt obtained in the step 1) is 1:0.5-1.5 in the step 2), the mass ratio of the covalent organic framework to the acid catalyst obtained in the step 1) is 1:2-4, the reaction temperature is 100-150 ℃ in the step 2), and the reaction time is 12-36 h.
  4. 4. The preparation method of the bidentate ligand supported covalent organic framework hydrogen evolution catalyst is characterized in that the mass ratio of the metal doped covalent organic framework obtained in the step 2) to the bidentate ligand is 1:0.5-1.5 in the step 3), the mass ratio of the metal doped covalent organic framework obtained in the step 2) to the acid catalyst is 1:2-4, the reaction temperature is 100-150 ℃ in the step 2), and the reaction time is 12-36 h.
  5. 5. The method for preparing a bidentate ligand-supported covalent organic framework hydrogen evolution catalyst according to claim 1, wherein the acid catalyst is glacial acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid or sulfuric acid; The organic solvent I is any two or three of mesitylene, N-dimethylformamide, dioxane, o-dichlorobenzene and N-butanol; The organic solvent II is any three or four of N, N-dimethylformamide, methanol, ethanol, acetone, tetrahydrofuran and deionized water.
  6. 6. The preparation method of the bidentate ligand-supported covalent organic framework hydrogen evolution catalyst is characterized in that the mass percentage concentration of sulfuric acid is 30% -40% or 95% -98%.
  7. 7. A bidentate ligand supported covalent organic framework hydrogen evolution catalyst prepared according to the method of any one of claims 1-6.
  8. 8. Use of a bidentate ligand supported covalent organic framework hydrogen evolution catalyst according to claim 7 as an electrocatalyst for the electrocatalytic decomposition of water hydrogen evolution.
  9. 9. The use according to claim 8, characterized by the steps of: 1) Polishing the L-shaped glassy carbon electrode by using polishing powder, washing and drying to obtain the L-shaped glassy carbon electrode for removing pollutants and eliminating physical defects; 2) Fully grinding the covalent organic framework hydrogen evolution catalyst supported by the bidentate ligand in an agate mortar, and then uniformly mixing the covalent organic framework hydrogen evolution catalyst supported by the bidentate ligand, a binder, absolute ethyl alcohol and water according to the mass ratio by ultrasound to obtain printing ink; 3) And (3) uniformly dripping the ink obtained in the step (2) on the L-shaped glassy carbon electrode obtained in the step (1), and drying under the irradiation condition of an infrared lamp to obtain the electrocatalytic decomposition water hydrogen evolution electrode.
  10. 10. The use according to claim 9, characterized in that in step 1) the L-shaped vitreous carbon electrode is polished with polishing powders of dimensions 1.0 μm, 0.3 μm, 0.05 μm in sequence; The mass ratio of the covalent organic framework hydrogen evolution catalyst supported by the bidentate ligand in the step 2) to the binder, the absolute ethyl alcohol and the water is (1-5): 0.01:100:100, and the binder in the step 2) is naphthol.

Description

Double-tooth ligand supported covalent organic framework hydrogen evolution catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of hydrogen evolution electrocatalyst, and in particular relates to a covalent organic framework hydrogen evolution catalyst supported by a bidentate ligand, and a preparation method and application thereof. Background The hydrogen energy is expected to replace fossil fuel by virtue of the characteristics of green, high heat value and low energy consumption. The hydrogen production by water electrolysis is a most important green hydrogen preparation method at present, and is paid attention to because of the advantages of low energy consumption, less greenhouse gas emission, high hydrogen purity, low impurity content and the like. The research of catalysts for hydrogen production by water electrolysis is primarily based on noble metals, and has high electrocatalytic activity, but the large-scale application is difficult to realize due to the rare reserves and high price. Therefore, the development of low-cost, high-electrocatalytic activity and stability non-noble metal catalysts is a very important and popular research field. The covalent organic framework is assembled by connecting the mechanism parts through strong covalent bonds, so that the covalent organic framework can show excellent chemical stability under severe electrochemical conditions. Due to the modular nature of covalent organic frameworks, pore structure and functional groups can be precisely tailored according to reticulation chemistry. Covalent organic frameworks are thus potential catalysts for electrocatalytic hydrogen evolution. In recent years, more and more researchers have performed electrochemical catalyst preparation work on covalent organic frameworks. For example, xingying Liu et al synthesized an electrocatalyst Co-Salen COF EDA using 1,3,5-TRIS (3 '-aldehyde-4' -hydroxyphenyl) benzene, ethylenediamine and cobalt salts that exhibited an overpotential of 320mV at a current density of 10 mA cm -2 (ADVANCED SCIENCE, 2022, 9:22). However, the above electrocatalytic properties are still not satisfactory for scientific and technical applications. Therefore, how to develop efficient electrocatalytic hydrogen evolution properties based on covalent organic frameworks is an important issue. The bidentate ligand replaces the adjacent layer structure formed by pi-pi stacking by a space expansion layer driven by coordination bonds, so that the stacked covalent organic framework layers are separated by the columns, and all catalytic sites accessible to the reaction are exposed, thereby improving the electrocatalytic hydrogen evolution activity. Therefore, for electrocatalytic hydrogen evolution studies, it is very interesting to increase the catalytic activity of the sites by opening the interlayer spacing with bidentate ligands, exposing more active sites. Disclosure of Invention In view of the problems existing in the prior art, the invention aims to provide a covalent organic framework hydrogen evolution catalyst supported by a bidentate ligand, a preparation method and application thereof, wherein a space expansion layer driven by a coordination bond can be used for replacing an adjacent layer structure formed by pi-pi stacking through the bidentate ligand support, so that more active sites are exposed, and meanwhile, the electrocatalytic performance is improved, and the obtained material has stronger electrocatalytic hydrogen production performance. In order to achieve the above purpose, the technical scheme of the invention is as follows: The invention provides a preparation method of a covalent organic framework hydrogen evolution catalyst supported by a bidentate ligand, which comprises the following steps: 1) Adding 1,3, 5-trimethyl phloroglucinol and o-phenylenediamine into an organic solvent I, uniformly mixing, then degassing, adding an acid catalyst for reaction after degassing, filtering the reacted material after the reaction is finished, and washing and drying the obtained filter solid by using an organic solvent II to obtain the covalent organic framework to be prepared; 2) Adding the covalent organic framework obtained in the step 1) and metal salt into an organic solvent I, uniformly mixing, then degassing, adding an acid catalyst for reaction after degassing, filtering the reacted material after the reaction is finished, washing the obtained filter solid by using an organic solvent II, and drying to obtain the metal-doped covalent organic framework to be prepared; 3) Adding the metal doped covalent organic framework and the bidentate ligand obtained in the step 2) into an organic solvent I, uniformly mixing, then degassing, adding an acid catalyst for reaction after degassing, filtering the reacted material after the reaction is finished, washing the obtained filter solid by the organic solvent II, and drying to obtain the covalent o