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ZnxCo1-x-ZIF-67 membrane and preparation method thereof

A technology of znxco1-x-zif-67 and ZIF-8, applied in the field of preparation of metal-organic framework membrane materials, can solve problems affecting compactness, integrity and gas separation performance, insufficient bonding between seeds and supports, and crystallinity. The problem of uneven particle size, etc., achieves the effect of excellent gas separation performance, great theoretical and practical significance, and low price.

Inactive Publication Date: 2019-04-16
BEIHANG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] Research results have shown that the preparation of Zn-doped Zn by secondary growth method x co 1-x -ZIF-67 membrane for C 3 h 6 and C 3 h 8 The test, the separation factor reached 50.5; ZIF-67 and Zn x co 1-x - ZIF-67 is not easy to nucleate directly on the surface of the support, and the size of the formed grains is uneven, especially a small amount of larger grains appear, which affects the grain orientation in the film, resulting in a non-dense film, and due to the The combination with the support is not strong enough, and the seed crystals are easy to fall off, which affect the compactness, integrity and gas separation performance of the ZnCo-ZIF-67 membrane

Method used

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  • ZnxCo1-x-ZIF-67 membrane and preparation method thereof

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Embodiment 1

[0045] The embodiment of the present invention provides a Zn x co 1-x -Preparation method of ZIF-67 film, such as figure 2 As shown, the specific steps are as follows:

[0046] Add an appropriate amount of Zn(NO 3 ) 2 ·6H 2 O and 2-methylimidazole (Hmim) were dissolved in deionized water respectively to form equal-volume solutions, and the two solutions were mixed, stirred evenly, and then placed in a polytetrafluoroethylene kettle as a reaction solution for growing ZIF-8, wherein two The molar ratio of valence zinc (Zn(II)) to Hmim is 1:72, and the concentration of Zn(II) is 9.5mmol / L. The porous alumina sheet-like supports that have been polished with sandpaper of different meshes were placed in the reaction solution, and reacted at 30° C. for 1 h. The sample was taken out, washed with deionized water several times and dried at room temperature to obtain a support with ZIF-8 seed crystals grown on the surface. The average size of the ZIF-8 seeds on the surface of the...

Embodiment 2

[0051] The embodiment of the present invention provides a Zn x co 1-x -The preparation method of ZIF-67 film, concrete steps are as follows:

[0052] The preparation process of the reaction solution for growing the seed layer and the molar ratio of divalent zinc (Zn(II)) to Hmim in the reaction solution, and the concentration of Zn(II) are all consistent with those in Example 1. The treated porous alumina sheet-like support was placed in the reaction solution, and reacted at 30° C. for 2 hours. The sample was taken out, washed with deionized water several times and dried at room temperature to obtain a support with ZIF-8 seed crystals grown on the surface, and the average size of the ZIF-8 seed crystals was about 1 μm. The support is placed on the growth Zn x co 1-x - In the reaction solution of ZIF-67, the preparation process and composition of the reaction solution are consistent with that of Example 1, reacted at 30°C for 8h, took out the sample, dried at room temperatu...

Embodiment 3

[0054] Adopt the conditions in embodiment 1 to grow ZIF-8 seed crystals on the support body surface, place it in the growth Zn x co 1-x -In the reaction solution of ZIF-67, wherein, the molar ratio of the total amount of divalent zinc (Zn(II)) and divalent cobalt (Co(II)) to Hmim is 1:72, Zn(II) and Co( The total concentration of II) is 10mmol / L, the molar ratio of Zn(II) to Co(II) is 3:1, react at 30°C for 8h, take out the sample, and dry at room temperature, the obtained Zn x co 1-x -The ZIF-67 film has defects under the scanning electron microscope, and there are gaps between the grains, and its H 2 / CO 2 , H 2 / N 2 , H 2 / CH 4 The separation coefficients are 4.3, 3.9, 2.7, which are lower than the ideal gas separation coefficient of the Knudsen diffusion mechanism, and the separation performance is poor.

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Abstract

The invention discloses a ZnxCo1-x-ZIF-67 membrane and a preparation method thereof, wherein the preparation method comprises the following steps of: growing a layer of ZIF-8 seed crystal on the surface of a porous support in advance, and using the ZIF-8 seed crystal as an induction core of the growth membrane to prepare a continuous ZnxCo1-x-ZIF-67 membrane; the prepared ZnxCo1-x-ZIF-67 membranecan be used in the technical field of H2 / CO2, H2 / N2, H2 / CH4 and other gas separation. According to the ZnxCo1-x-ZIF-67 membrane and a preparation method thereof, the ZIF-8 crystal grains grow on the surface of the porous support body to be used as the seed crystal for growing the ZnxCo1-x-ZIF-67 film, so that the problem that the seed crystal is easy to fall off due to insufficient bonding strength of the seed crystal layer and the porous support body can be effectively solved; and the preparation conditions adopted by the method are mild, the process is simple and controllable, the prepared ZnxCo1-x-ZIF-67 film has stable chemical structure and performance, excellent gas separation performance, wide application prospect and great theoretical and practical significance.

Description

technical field [0001] The invention relates to a method for preparing a metal-organic framework membrane material applied to high-performance gas separation, in particular to a Zn x co 1-x - ZIF-67 film and method for its preparation. Background technique [0002] Since entering the 21st century, more and more global problems have affected people's lives, such as the greenhouse effect, environmental pollution, energy shortage, etc. These problems are closely related to people's lives. Most of the energy currently used is fossil fuel energy. However, with the increase of the global population, the demand for energy is increasing. In addition, the consumption of energy makes fossil energy less and less. Therefore, countries around the world Beginning to attach importance to the development of sustainable energy and the protection of the environment, many countries have carried out a lot of research in the fields of hydrogen energy and solar energy and other new energy sourc...

Claims

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Application Information

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IPC IPC(8): B01D71/06B01D69/10B01D67/00B01D53/22
CPCB01D53/228B01D67/0006B01D69/10B01D71/06
Inventor 谷景华李泽耀
Owner BEIHANG UNIV
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