CN-117379988-B - Metal hydroxide organic framework composite film and preparation method and application thereof

Abstract

The invention relates to the technical field of composite materials, in particular to a metal hydroxide organic frame composite film, a preparation method and application thereof, wherein nickel chloride hexahydrate, terephthalic acid and N, and mixing and dissolving N-dimethylformamide, absolute ethyl alcohol and deionized water, pouring the mixture into a reaction kettle, putting an AAO film with the aperture of 160-200 nm into a mold for enabling one side of the film to contact with a reaction solution, putting the mold into the reaction kettle, and taking out the AAO film after reaction in the mold to obtain the composite film. The composite film has negative charge on the surface, so that it has excellent cation selectivity, and the MHOF layer of nano window cavity pore structure can be used as ion filter and conductor for raising ion selectivity, and the ion can pass through MHOF pore channel to raise its flux, and the highly ordered AAO nano channel is ion storage layer, so that it has the action of raising ion transmission. The maximum output power density of the composite membrane is higher than the commercial application standard, and the composite membrane can be applied to salt difference power generation.

Inventors

• WANG JIAN
• ZENG HUAN
• WU CAIQIN
• YAO CHENLING
• WANG DI
• MA WENBO

Assignees

• 成都理工大学

Dates

Publication Date

20260508

Application Date

20231103

Claims (8)

1. 1. A preparation method of a metal hydroxide organic frame composite membrane is characterized in that nickel chloride hexahydrate, terephthalic acid, N-dimethylformamide, absolute ethyl alcohol and deionized water are mixed and dissolved and then poured into a reaction kettle, an AAO membrane with the aperture of 160-200 nm is placed into a mold enabling one side of the membrane to contact a reaction solution, the mold with the AAO membrane placed therein is placed into the reaction kettle and reacted for 10-14 h at the temperature of 115-130 ℃, and the AAO membrane after the reaction in the mold is taken out to obtain the metal hydroxide organic frame composite membrane Ni 2 (OH) 2 @AAO.
2. 2. The preparation method of the metal hydroxide organic frame composite membrane according to claim 1 is characterized in that the reaction raw materials comprise, by weight, 80-120 parts of nickel chloride hexahydrate, 80-120 parts of terephthalic acid, 10-25 parts of N, N-dimethylformamide, 0.5-1.5 parts of absolute ethyl alcohol and 0.8-1.2 parts of deionized water.
3. 3. The method for preparing a metal hydroxide organic frame composite membrane according to claim 1, wherein the material of the reaction kettle and the mold is polytetrafluoroethylene.
4. 4. The method for preparing a metal hydroxide organic framework composite membrane according to claim 1, wherein the specific operation of placing the AAO membrane into a mold for contacting a single side of the membrane with a reaction solution is as follows: S1, preparing a die, namely taking two polytetrafluoroethylene plates with the same size, wherein a round hole is formed in the middle of one polytetrafluoroethylene plate; s2, packaging, namely cutting the AAO film to be the same as the polytetrafluoroethylene plates in size, respectively washing the AAO film with absolute ethyl alcohol and deionized water, placing the AAO film between the two polytetrafluoroethylene plates, enabling the front surface of the AAO film to face the open pore, and sealing the peripheries of the two polytetrafluoroethylene plates by using polytetrafluoroethylene adhesive tapes.
5. 5. The method for preparing the metal hydroxide organic frame composite membrane according to claim 1, further comprising the step of post-treatment, wherein the method is characterized in that the AAO membrane after reaction in a die is taken out, is repeatedly washed by N, N-dimethylformamide and absolute ethyl alcohol respectively, is soaked in the N, N-dimethylformamide for 1.5-3 hours, is soaked in ethanol solution for overnight, and is finally dried at the temperature of 45-55 ℃.
6. 6. The preparation method of the metal hydroxide organic frame composite membrane according to claim 1 is characterized by further comprising the step of recovering a reaction solution, wherein the reaction solution is poured into a centrifuge tube, centrifuged for 4-6 min under the condition of 9000-12000 rpm, light green precipitate is collected, the precipitate is centrifugally washed by absolute ethyl alcohol under the same condition, and finally the centrifugally washed precipitate is dried for 10-12 h at 60-70 ℃ to obtain Ni 2 (OH) 2 powder.
7. 7. A metal hydroxide organic framework composite membrane prepared by the method of any one of claims 1-6.
8. 8. The use of a metal hydroxide organic framework composite membrane according to claim 7 in salt-differential power generation.

Description

Metal hydroxide organic framework composite film and preparation method and application thereof Technical Field The invention relates to the technical field of composite materials, in particular to a metal hydroxide organic framework composite film, a preparation method and application thereof. Background With the growth of world population and the development of industry, the demand for energy is continuously increased, and the search for efficient and environment-friendly renewable energy is very important. The salt difference energy is also called blue energy or osmotic energy, is stored in the salinity gradient between seawater and fresh water or between seawater with different salt concentration, and stores huge energy. Compared with other ocean energy, the energy source has higher stability and is one energy source with the largest energy density in the ocean energy. Is a renewable clean energy source with great development potential, and is receiving a great deal of attention as a solution to the energy problem. Porous crystalline materials such as Metal Organic Frameworks (MOFs), covalent Organic Frameworks (COFs) and hydrogen-bonded organic frameworks (HOFs) have also received great attention in salt-differential power generation due to their high porosity, unique pore structure, adjustable pore size and geometry, modifiable surfaces, and the like. The Metal Hydroxide Organic Frameworks (MHOFs) are novel crystalline porous materials formed from transition metal oxides and MOFs by reacting layered hydroxides with aromatic carboxylate linkers, the stability of which is uniquely enhanced by the presence of strong pi-pi stacking interactions. These unique characteristics make it of great application potential in salt-differential power generation. In recent years, several methods of obtaining salt differential energy in salinity gradients have been proposed, currently mainly by two methods, pressure Retarded Osmosis (PRO) and Reverse Electrodialysis (RED) based on the action of ion-selective osmosis membranes. From previous studies, it is known that the electrodialysis reversal technique has the main advantage of directly converting the energy in the salinity gradient into electric energy with higher energy conversion efficiency compared with the pressure delay osmosis technique. Ion exchange membranes are key factors in extracting salinity gradient energy using RED technology, where ion selectivity and ion flux determine the power density produced during conversion. However, in RED technology, the conventional ion exchange membrane which can be used for obtaining the salt difference has some defects, which limit the application of the ion exchange membrane. If the preparation method is complex, the mechanical property is poor, the ion selectivity is low, the internal resistance of the membrane is overlarge, the ion flux is low, the stability is poor, and the like, the problems of low energy conversion efficiency and power density are caused, and the commercial standard cannot be achieved. Disclosure of Invention The invention aims to overcome the defects of the prior art and provides a metal hydroxide organic framework composite membrane and a preparation method and application thereof. The preparation method of the metal hydroxide organic frame composite membrane comprises the following steps of mixing and dissolving nickel chloride hexahydrate, terephthalic acid, N-dimethylformamide, absolute ethyl alcohol and deionized water, pouring the mixed solution into a reaction kettle, placing an AAO membrane with the aperture of 160-200 nm into a mold which enables one side of the membrane to be in contact with a reaction solution, placing the mold with the AAO membrane into the reaction kettle, reacting for 10-14 h at the temperature of 115-130 ℃, and taking out the AAO membrane after the reaction in the mold to obtain the metal hydroxide organic frame composite membrane Ni 2(OH)2 @AAO. Further, the reaction raw materials comprise, by weight, 80-120 parts of nickel chloride hexahydrate, 80-120 parts of terephthalic acid, 10-25 parts of N, N-dimethylformamide, 0.5-1.5 parts of absolute ethyl alcohol and 0.8-1.2 parts of deionized water. Further, the material of the reaction kettle and the mold is polytetrafluoroethylene. Further, the AAO film is put into a mold that brings one side of the film into contact with the reaction solution in the following specific operations: S1, preparing a die, namely taking two polytetrafluoroethylene plates with the same size, wherein a round hole is formed in the middle of one polytetrafluoroethylene plate, S2, packaging, namely cutting an AAO film to be the same as the polytetrafluoroethylene plates in size, respectively washing the AAO film with absolute ethyl alcohol and deionized water, placing the AAO film between the two polytetrafluoroethylene plates, enabling the front face of the film to face towards the open hole, and sealing the periphery of the two polytetrafluor