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CN-121974295-A - Preparation method of MOFs hydrogen storage material synthesized in situ and hydrogen storage material

CN121974295ACN 121974295 ACN121974295 ACN 121974295ACN-121974295-A

Abstract

The invention belongs to the technical field of hydrogen storage material preparation, and provides a preparation method of MOFs hydrogen storage material synthesized in situ and a hydrogen storage material, wherein ZrCl4 and HCl with certain mass are mixed, and the mixture is stirred for a first set period of time at room temperature at a preset rotating speed; adding solvent and ligand into the mixed solution of ZrCl4 and HCl after stirring, stirring for a second set period of time at a preset rotating speed, and placing the mixed solution of solvent and ligand into a polytetrafluoroethylene reaction bottle for heating reaction to obtain MOFs hydrogen storage material. In the synthesis of UIO-67, HCl and ZrCl 4 are added in advance to be mixed, so that ZrCl 4 is subjected to Cl ‑ auxiliary pre-hydrolysis at room temperature instantly to generate a metal cluster, a metal framework is locked, reversible Cl ‑ is used for occupying space, cl ‑ is subjected to accurate exchange crystallization with long-chain 4, 4-diphthalic acid, the problems of lattice defects and large difference of specific surface area batches caused by different nucleation growth rates are thoroughly solved, meanwhile, zr 4+ hydrolysis and precipitation are simultaneously inhibited in a strong acid environment, the yield of a single kettle is doubled, and the stability and hydrogen storage performance of the material are ensured.

Inventors

  • YU HAIMENG
  • ZHANG CHUNXIA
  • LIU JIANMIN
  • WANG AILING
  • CAO HONGZHEN
  • ZHANG JIBING
  • LI XIN
  • WANG HUI
  • ZHANG LIANGCHEN
  • Dan Shaopeng

Assignees

  • 山东电力工程咨询院有限公司

Dates

Publication Date
20260505
Application Date
20251222

Claims (10)

  1. 1. The preparation method of the MOFs hydrogen storage material synthesized in situ is characterized by comprising the following steps: mixing ZrCl4 and HCl, and stirring at a preset rotating speed for a first set period of time at room temperature; Adding a solvent and a ligand into the mixed solution of ZrCl4 and HCl after stirring, and stirring for a second set period of time at a preset rotating speed; and (3) placing the mixed solution added with the solvent and the ligand into a polytetrafluoroethylene reaction bottle for heating reaction to obtain the MOFs hydrogen storage material.
  2. 2. The method for preparing in situ synthesized MOFs hydrogen storage material of claim 1 wherein the molar ratio of ZrCl 4 to HC is from 5:1 to 5:3.
  3. 3. The method for preparing in situ synthesized MOFs hydrogen storage material according to claim 1 wherein ZrCl 4 and HCl are added to a reaction flask and mixed first, and stirred at 800rmp for 5min at room temperature.
  4. 4. The method for preparing in situ synthesized MOFs hydrogen storage material according to claim 1, wherein the solvent is methanol, ethanol, DMF and/or water.
  5. 5. The method for preparing MOFs hydrogen storage material synthesized in situ according to claim 4, the method is characterized in that the solvent is DMF.
  6. 6. The method for preparing in situ synthesized MOFs hydrogen storage material according to claim 1, wherein said ligand is 4, 4-biphenyl dicarboxylic acid.
  7. 7. The method for preparing MOFs hydrogen storage material synthesized in situ according to claim 1, wherein 300mM LDMF and 4, 4-diphthalic acid are added into the mixed solution of ZrCl4 and HCl after stirring, stirring is carried out for 30min at a speed of 800rmp, and the molar ratio of ZrCl 4 to 4, 4-diphthalic acid is 1:1.5.
  8. 8. The method for preparing MOFs hydrogen storage materials synthesized in situ according to claim 1, wherein the mixed solution of the added solvent and the ligand is transferred into a polytetrafluoroethylene reaction bottle, and the reaction bottle is placed in an electrothermal blowing drying oven to be heated to 120 ℃ for reaction for 24 hours.
  9. 9. The method for preparing MOFs hydrogen storage materials synthesized in situ according to claim 1, wherein the solution after the heating reaction is cooled to room temperature, the solvent is removed by filtration, the solid product is washed by DMF and ethanol in sequence, and the solid product is heated to 80 ℃ in an oven and is fully dried to obtain the MOFs hydrogen storage materials.
  10. 10. An in situ synthesized MOFs hydrogen storage material, characterized in that it is obtained by the method for preparing an in situ synthesized MOFs hydrogen storage material according to any one of claims 1 to 9.

Description

Preparation method of MOFs hydrogen storage material synthesized in situ and hydrogen storage material Technical Field The invention belongs to the technical field of hydrogen storage material preparation, and particularly relates to a preparation method of MOFs hydrogen storage material synthesized in situ and the hydrogen storage material. Background The physical adsorption type hydrogen storage adsorbs and stores the gas through intermolecular interaction between the adsorbent and the gas, the adsorption process has high reversibility, and the adsorption materials have high hydrogen storage capacity. Among them, MOFs porous materials have been ideal materials for non-dissociated hydrogen storage due to their uniform pore structure and adjustable pore size, high porosity, large specific surface area and low density. The specific surface area and the porosity of MOFs provide larger adsorption space, but high-efficiency adsorption sites are generally lacking, and particularly, in the conventional preparation method of MOFs hydrogen storage materials, the problems of lattice defects, larger specific surface area batch difference and the like caused by different nucleation growth rates can occur in the UiO-67 synthesis, so that the stability and the hydrogen storage performance of the materials are affected. The method is mainly characterized in that lattice defects influence the stability and hydrogen storage performance of the material, and the adsorption capacity of the high specific surface area batch can be improved due to more micropores, but the overlarge difference can reflect the instability of the synthesis process, the lattice defects or the blocking of pore canals are introduced, and the utilization rate of effective adsorption sites is reduced. Disclosure of Invention In order to solve the problems, the invention provides a preparation method of MOFs hydrogen storage materials synthesized in situ and the hydrogen storage materials, HCl and ZrCl 4 are mixed in advance, so that the ZrCl 4 is instantly completed with the assistance of Cl - for pre-hydrolysis to generate metal clusters, a metal framework is locked, reversible Cl - occupies a position, and Cl - is precisely exchanged and crystallized with long-chain 4, 4-biphenyl dicarboxylic acid, so that the problems of lattice defects and large batch difference of specific surface areas caused by different nucleation growth rates are thoroughly solved. In order to achieve the above object, in a first aspect, the present invention provides a preparation method of MOFs hydrogen storage materials by in-situ synthesis, which adopts the following technical scheme: A preparation method of MOFs hydrogen storage material synthesized in situ comprises the following steps: mixing ZrCl4 and HCl, and stirring at a preset rotating speed for a first set period of time at room temperature; adding a solvent and a ligand into the ZrCl4 and HCl mixed solution after stirring, and stirring for a second set period of time at a preset rotating speed; and (3) placing the mixed solution added with the solvent and the ligand into a polytetrafluoroethylene reaction bottle for heating reaction to obtain the MOFs hydrogen storage material. Further, the molar ratio of ZrCl 4 to HC is 5:1-5:3. Further, zrCl 4 and HCl were added to the reaction flask and mixed first, and stirred at 800rmp for 5min at room temperature. Further, the solvent is methanol, ethanol, DMF and/or water. Further, the solvent is DMF. Further, the ligand is 4, 4-biphenyl dicarboxylic acid. Further, 300 mM of LDMF and 4, 4-diphthalic acid are added into the ZrCl4 and HCl mixed solution after stirring, and the mixed solution is stirred for 30min at a rotating speed of 800rmp, wherein the molar ratio of ZrCl 4 to 4, 4-diphthalic acid is 1:1.5. Further, the mixed solution added with the solvent and the ligand is transferred into a polytetrafluoroethylene reaction bottle, and the reaction bottle is placed in an electrothermal blowing drying oven to be heated to 120 ℃ for reaction for 24 hours. And further, cooling the solution after the heating reaction to room temperature, filtering to remove the solvent, washing the solid product by using DMF and ethanol in sequence, heating to 80 ℃ in an oven, and fully drying to obtain the hydrogen storage MOFs material. In order to achieve the above object, in a second aspect, the present invention further provides an in-situ synthesized MOFs hydrogen storage material, which adopts the following technical scheme: An in situ synthesized MOFs hydrogen storage material obtainable by the method of preparing an in situ synthesized MOFs hydrogen storage material as described in the first aspect. Compared with the prior art, the invention has the beneficial effects that: 1. In the synthesis of UIO-67, HCl and ZrCl 4 are added in advance to be mixed, so that ZrCl 4 is subjected to Cl - auxiliary pre-hydrolysis at room temperature instantly to generate a metal cluster, a metal frame