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CN-122011413-A - Copper-based metal organic framework material and preparation method and application thereof

CN122011413ACN 122011413 ACN122011413 ACN 122011413ACN-122011413-A

Abstract

The invention discloses a copper-based metal organic framework material, a preparation method and application thereof, wherein the molecular formula of the copper-based metal organic framework material is [ Cu 2 (TPPE)(μ 2 -H 2 O) 2 ]; TPPE represents deprotonated 1, 2-tetra (4- (1H-pyrazol-4-yl) phenyl) ethylene, and each asymmetric unit in the copper-based metal organic framework material comprises 1 Cu 2+ ion, 1/2 completely deprotonated TPPE 4‑ ligand and 1 bridging mu 2 -H 2 O molecule. The invention constructs a novel metal organic framework material with bridged water molecules, which can realize trace ammonia capture under low pressure and has excellent stability in strong alkali environment.

Inventors

  • Mo Zongwen
  • LU SHUANG
  • Long Zhujun

Assignees

  • 五邑大学

Dates

Publication Date
20260512
Application Date
20260211

Claims (10)

  1. 1. A copper-based metal-organic framework material, characterized in that the molecular formula of the copper-based metal-organic framework material is [ Cu 2 (TPPE)(μ 2 -H 2 O) 2 ];TPPE 4- represents deprotonated 1, 2-tetrakis (4- (1H-pyrazol-4-yl) phenyl) ethylene ], in which each asymmetric unit comprises 1 Cu 2+ ion, 1/2 completely deprotonated TPPE 4- ligand and 1 bridged μ 2 -H 2 O molecule.
  2. 2. The copper-based metal-organic framework material according to claim 1, wherein the crystal structure of the copper-based metal-organic framework material belongs to monoclinic system, P2/m space group, and the crystallographic data is as follows ：a = 11.9568(3) Å;b = 16.2011(3) Å;c = 14.1530(4) Å;α= 90°;β= 106.510(3)°;γ= 90°;V= 2628.59(12) Å 3 ;Z = 2.
  3. 3. The copper-based metal-organic framework material according to claim 1 or 2, characterized in that in the copper-based metal-organic framework material Cu 2+ has three coordination modes, wherein the occupancy of Cu1, cu2 and Cu3 is 0.25,0.5,0.25, respectively, cu1 and Cu2 all form an octahedral configuration with six coordinates to the N atoms of 4 TPPE 4- ligands and 2 μ 2 -H 2 O molecules with an occupancy of 0.5, cu3 forms a planar tetragonal configuration with the N atoms of 4 different TPPE 4- ligands.
  4. 4. A method of preparing a copper-based metal organic framework material according to any one of claims 1 to 3, comprising the steps of: Mixing copper salt, 1, 2-tetra (4- (1H-pyrazol-4-yl) phenyl) ethylene, a solvent and water to obtain a mixed solution, and carrying out solvothermal reaction on the mixed solution to obtain the compound.
  5. 5. The method according to claim 4, wherein the molar ratio of the 1, 2-tetrakis (4- (1H-pyrazol-4-yl) phenyl) ethylene to the copper salt is (2 to 3.3): 1.
  6. 6. The method according to claim 4, wherein the solvothermal reaction temperature is 90 ℃ to 150 ℃.
  7. 7. The method of claim 4, wherein the solvothermal reaction time is 12 h-24: 24 h.
  8. 8. The method of claim 4, wherein the copper salt comprises copper nitrate.
  9. 9. An adsorbent comprising the copper-based metal-organic framework material according to any one of claims 1 to 3.
  10. 10. Use of the copper-based metal organic framework material of any one of claims 1 to 3, or the adsorbent of claim 9 for adsorbing ammonia gas.

Description

Copper-based metal organic framework material and preparation method and application thereof Technical Field The present invention relates to metalsThe technical field of organic frame materials, in particular to a copper-based metal organic frame material and a preparation method and application thereof. Background Since the application of the haber-bosch process in industry in 1908, ammonia has become one of the most widely used inorganic chemicals with annual yields exceeding 2 million tons. Ammonia is of paramount importance in industries such as petrochemicals, metal manufacturing, paper making, textiles, and agriculture. However, despite the economic advantages of ammonia, nitrogen emissions present significant environmental and health risks. Ammonia is one of the widely used inorganic chemicals, but its strong irritation and corrosiveness are listed in the list of dangerous chemicals, especially in the environment where ammonia is not easily detected at low concentration with an olfactory threshold of 5-50 ppm, it can cause potential harm such as olfactory fatigue, respiratory tract injury, consciousness loss, etc., and the national detection standard for ammonia is 20 mg/m 3, and long-term exposure to ammonia environment can cause respiratory tract injury, consciousness loss, and even cardiopulmonary dysfunction. Researchers have been working on exploring suitable materials suitable for the ammonia adsorption field such as traditional porous materials like activated carbon, mesoporous silica and zeolite, and emerging adsorbents like metal organic framework materials, hydrogen bonded organic frameworks and covalent organic framework materials, porous polymers, etc. porous have received widespread attention in recent years for their application in ammonia physisorption and chemisorption. Although ammonia adsorption technology has been well developed at high concentrations, capturing ammonia molecules at low concentrations remains a critical issue. Compared with the existing method for absorbing ammonia under high concentration, the method has the advantages that materials with stronger interaction force on ammonia under lower pressure and trace ammonia capture can be realized without limited corrosion of ammonia are necessary to be developed. Disclosure of Invention The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the first aspect of the present invention proposes a copper-based metal-organic framework material having excellent stability, capable of achieving trace ammonia capture at low pressure. The second aspect of the invention also provides a method for preparing the copper-based metal organic framework material. The third aspect of the present invention also provides an adsorbent. The fourth aspect of the invention also provides the use of a copper-based metal organic framework material. According to a first aspect of the present invention there is provided a copper-based metal-organic framework material of the formula [ Cu 2(TPPE)(μ2-H2O)2];TPPE4- represents deprotonated 1, 2-tetrakis (4- (1H-pyrazol-4-yl) phenyl) ethylene ], in which each asymmetric unit comprises 1 Cu 2+ ion, 1/2 fully deprotonated TPPE 4- ligand and 1 bridging μ 2-H2 O molecule. According to a preferred embodiment of the invention, the crystal structure of the copper-based metal-organic framework material belongs to the monoclinic system, the P2/m space group, and the crystallographic data are as follows ：a = 11.9568(3) Å;b = 16.2011(3) Å;c = 14.1530(4) Å;α= 90°;β= 106.510(3)°;γ= 90°;V= 2628.59(12) Å3;Z = 2. According to a preferred embodiment of the present invention, cu 2+ has three coordination modes in the copper-based metal-organic framework material. Wherein the occupancy of Cu1, cu2 and Cu3 is 0.25,0.5,0.25 respectively. Cu1 and Cu2 form octahedral configuration with six coordination and 4N atoms of TPPE 4- ligands and 2 mu 2-H2 O molecules with the occupancy of 0.5, and Cu3 and 4N atoms of different TPPE 4- ligands form planar quadrilateral configuration. The copper-based metal organic framework material according to the embodiment of the invention has at least the following beneficial effects: the invention constructs a novel metal organic framework material with bridged water molecules, which can also have excellent stability in strong alkaline environment, and in addition, the ammonia gas can be captured in trace amount under low pressure because of larger pores in the material structure and the bridging water molecules in the framework to have a hydration mechanism. According to a second aspect of the present invention there is provided a method of preparing a copper-based metal organic framework material as in the first aspect of the present invention, comprising the steps of: Mixing copper salt, 1, 2-tetra (4- (1H-pyrazol-4-yl) phenyl) ethylene, a solvent and water to obtain a mixed solution, and carrying out solvothermal reaction on the mixed so