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CN-117654642-B - Metal organic framework composite material and preparation method and application thereof

CN117654642BCN 117654642 BCN117654642 BCN 117654642BCN-117654642-B

Abstract

The invention discloses a metal organic frame composite material, a preparation method and application thereof, wherein the preparation method comprises the steps of adding a metal source and an organic ligand source containing hydrazine hydrate into a solvent, stirring uniformly, then reacting for 5-7h at 120-140 ℃, separating to obtain the metal organic frame material, immersing the heated and activated metal organic frame material in SrTiO 3 :Al suspension, and drying. The metal organic frame composite material prepared by the invention has excellent hydrophilicity and adsorption energy, rich water molecule adsorption sites, unique pore structure in the structure and large-area contact with air, adsorbed water molecules are rapidly released under the drive of sunlight and flow through the surface of SrTiO 3 :Al, and the surface of the SrTiO 3 :Al is filled in a closed environment in a gaseous state, so that the construction of the metal organic frame composite material opens up a sustainable way for producing green hydrogen by only utilizing in-situ resources in natural environment in extreme environment.

Inventors

  • LIU MAOCHANG
  • SHAN XUELI
  • SHI JINWEN

Assignees

  • 西安交通大学苏州研究院

Dates

Publication Date
20260512
Application Date
20231117

Claims (7)

  1. 1. A preparation method of a metal organic frame composite material is characterized in that the metal organic frame material after heating and activating is immersed in a methanol suspension of SrTiO 3 Al photocatalyst, and the metal organic frame composite material is obtained after drying treatment; Adding a metal source and an organic ligand source containing hydrazine hydrate into a solvent, uniformly stirring, then reacting at 120-140 ℃ for 5-7 h, separating to obtain the metal organic frame material, wherein the metal source is zirconium chloride octahydrate, and the organic ligand source containing hydrazine hydrate is fumaric acid and hydrazine hydrate; the heating and activating conditions are that under vacuum, 10-14 h is kept at 50-80 ℃ and then 22-26 h is kept at 130-170 ℃; the drying condition is that stirring in oil bath, and drying at 50-70deg.C for 10-12 h.
  2. 2. The process according to claim 1, wherein the ratio of fumaric acid to hydrazine hydrate is 12.5 mmol/0.1-0.5 mL and the molar ratio of fumaric acid to metal source is 1/1.
  3. 3. The method according to claim 1, wherein the solvent is a mixture of N, N '-dimethylformamide and formic acid, and the volume ratio of N, N' -dimethylformamide to formic acid is 50:10-25.
  4. 4. The preparation method according to claim 1, wherein the mass ratio of the metal organic framework material to the SrTiO 3 /Al photocatalyst is 100-60:0-40, and the use amount of the SrTiO 3 /Al photocatalyst does not include 0.
  5. 5. The preparation method of the SrTiO 3 Al photocatalyst according to claim 4, wherein the preparation method of the SrTiO 3 Al photocatalyst comprises the following steps: 1) Grinding and mixing the mixture of SrTiO 3 、SrCl 2 ∙6H 2 O and Al 2 O 3 uniformly, and calcining in 1273-1473K air for 4-8 hours to obtain SrTiO 3 Al precursor, wherein the molar ratio of SrTiO 3 、SrCl 2 ∙6H 2 O to Al 2 O 3 is 1-2:9-11:0.01-0.04; 2) Adding a SrTiO 3 Al precursor into a mixed solution of H 2 O and methanol, then adding a Rh source and uniformly dispersing by using ultrasonic waves; 3) Then, transferring the mixed solution obtained in the step 2) into a reactor, discharging air, then adding a Cr source, irradiating for 1-3 hours by using a Xe lamp, centrifuging, washing and drying the reaction solution after the reaction is finished to obtain SrTiO 3 Al photocatalyst; wherein the Rh source is Na 3 RhCl 6 , the mass of Rh contained in the Rh source accounts for 0.6wt% -0.8wt% of the mass of the SrTiO 3 and the Cr source is K 2 CrO 4 , and the mass of Cr contained in the Cr source accounts for 0.5-1 wt% of the mass of the SrTiO 3 .
  6. 6. A metal organic framework composite material, characterized in that it is produced by the preparation method according to any one of claims 1-5.
  7. 7. Use of the metal-organic framework composite material of claim 6 for in situ air hydrogen production.

Description

Metal organic framework composite material and preparation method and application thereof Technical Field The invention belongs to the technical field of catalytic hydrogen production, and particularly relates to a metal organic framework composite material, a preparation method thereof and application thereof in-situ air hydrogen production. Background The energy shortage crisis caused by traditional fossil energy consumption and liquid fuel shortage, especially in remote areas, has prompted us to explore renewable and pollution-free alternative energy sources. Hydrogen is an excellent energy carrier and an excellent clean renewable energy source due to its high energy density, clean combustion products, excellent storage and transport properties, and high conversion and utilization efficiency, and is considered as an important bridge connecting fossil energy sources to renewable energy sources. Solar energy is an inexhaustible clean resource, and the solar energy is an ideal energy conversion way for producing hydrogen by driving and decomposing water. However, conventional photocatalytic water splitting systems are geographically limited by the supply of fresh water. Typically, their operation depends on the periodic replenishment of liquid water, and the resulting transportation creates additional resource consumption, which involves a series of complex environmental, economic and regulatory problems. In addition, fresh water shortages due to climate change, global population growth and industry development have become a serious global challenge. Atmospheric water, about 13 trillion liters of continuously clean water, is a vast source of untapped sustainable fresh water. Solar-driven adsorption-based atmospheric water collection (SAWH) can effectively address the global freshwater resource crisis by providing geographically unlimited decentralized water collection. In order to cope with the current severe energy crisis and fresh water crisis, the method for preparing hydrogen by decomposing air water through photocatalysis by only utilizing in-situ resources such as air water, solar energy and the like is a green scientific method. Current reports on air hydrogen production focus primarily on hydrogen production by electrocatalytic or photoelectrocatalytic utilization of captured atmospheric water. However, these require the intervention of an intermediate energy source, electric energy, which causes waste after multiple energy conversions. The photocatalytic decomposition of atmospheric water to produce hydrogen not only eliminates the need for secondary energy supply and realizes hydrogen production without regional limitation, but also can relieve the water shortage crisis. In addition, the technology has the advantages of simple steps, mild reaction conditions, low cost, easy large-scale development and the like, and is considered as the most attractive renewable energy hydrogen production path. Therefore, the initiation and development of the photocatalytic decomposition of atmospheric water to produce hydrogen are urgent. Considering the practicability of photocatalytic decomposition of atmospheric water to produce hydrogen in drought environment, the hydrogen production performance of the hydrogen production device is greatly dependent on the material characteristics. Conventional adsorbents such as silica gel, zeolite, activated carbon, and the like have a strong affinity for water making their regeneration energy intensive. Metal Organic Frameworks (MOFs) are a new generation of porous materials composed of metal nodes and organic ligands by self-assembly, known for their unique porosity, synthesis tunability, and resultant chemical and structural diversity, ideal materials for regulating water adsorption kinetics and thermodynamics. SrTiO 3 Al is taken as a photocatalyst, and breakthrough progress is made in the field of ultraviolet light catalytic decomposition of water. Disclosure of Invention The invention aims to overcome the defects of the prior art and provides a metal-organic framework composite material, a preparation method and application thereof. The technical scheme of the invention is as follows: The invention relates to a preparation method of a metal organic frame composite material, which comprises the steps of immersing a heated and activated metal organic frame material in SrTiO 3:Al suspension, and drying to obtain the metal organic frame composite material. Preferably, the metal organic framework material (MOF-801 (N)) is prepared by adding a metal source and an organic ligand source containing hydrazine hydrate into a solvent, uniformly stirring, then reacting for 5-7h at 120-140 ℃, and separating to obtain the metal organic framework material. Preferably, the metal source is zirconium chloride octahydrate. Preferably, the organic ligand source containing hydrazine hydrate is fumaric acid and hydrazine hydrate, the dosage ratio of the fumaric acid to the hydrazine hydrate