Manufacturing method of metal organic framework

Abstract

The invention provides a manufacturing method of a metal organic framework, and the manufacturing method of the metal organic framework comprises the steps: obtaining the feature information of an original metal organic framework, and constructing an initial framework structure according to the feature information, the feature information comprising the number of atoms in the original metal organic framework, the size of a pore diameter and the length of a pore channel; determining the components of the synthetic reagent according to the material of the preset skeleton; obtaining a liquid mixture, and mixing the liquid mixture with a synthetic reagent under a preset condition to obtain a mixed solution; mixing the mixed solution with the initial skeleton structure, and drying at a preset temperature to obtain a metal organic skeleton; the problem that in the prior art, a metal organic framework is limited in carbon dioxide adsorption capacity is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of carbon dioxide capture, and in particular to a method for manufacturing a metal organic framework. Background Art

[0002] In the prior art, carbon dioxide is adsorbed mainly through the structure of a metal organic framework, but the adsorption capacity of the metal organic framework structure is limited. The metal organic framework is a porous material with a regular pore structure that can selectively adsorb or exclude molecules according to the size of the molecules. Summary of the invention

[0003] The main purpose of the present invention is to provide a method for preparing a metal organic framework to solve the problem of limited absorption capacity of the metal organic framework for carbon dioxide in the prior art.

[0004] In order to achieve the above object, according to one aspect of the present invention, a method for preparing a metal organic framework is provided, and the method for preparing the metal organic framework comprises:

[0005] Acquiring characteristic information of the original metal organic framework and constructing an initial framework structure based on the characteristic information, wherein the characteristic information includes the number of atoms in the original metal organic framework, the size of the pores, and the length of the pores;

[0006] Determine the composition of the synthetic reagent according to the material of the preset skeleton;

[0007] obtaining a liquid mixture, and mixing the liquid mixture with a synthetic reagent under preset conditions to obtain a mixed solution;

[0008] The mixed liquid is mixed with the initial framework structure and dried at a preset temperature to obtain a metal organic framework.

[0009] Furthermore, before obtaining the liquid mixture step, the step further includes:

[0010] irradiating the synthesis reagent with an X-ray diffractometer to obtain a first spectrum;

[0011] Acquire a standard spectrum, and calculate a first difference between each peak in the first spectrum and a corresponding peak in the standard spectrum;

[0012] When it is determined that the first difference is within the first preset range, it indicates that the metal organic framework structure produced according to the synthesis reagent is complete.

[0013] Furthermore, the preparation method also includes:

[0014] When it is determined that the first difference is not within the first preset range, it indicates that the metal organic framework structure produced according to the synthesis reagent is incomplete.

[0015] Further, after the step of determining that the first difference is not within the first preset range, the method further includes:

[0016] irradiating the synthesis reagent with a scanning electron microscope to obtain a second spectrum, wherein the second spectrum is used to characterize the degree of incompleteness of the metal organic framework produced by the synthesis reagent;

[0017] When it is determined that the degree of incompleteness is within a first set range, the first preset condition for preparing the synthetic reagent is changed, and the first preset condition includes temperature, pressure and time.

[0018] Furthermore, the preparation method also includes:

[0019] When the degree of incompleteness is judged to be outside the first set range, the synthesis reagent is irradiated with an X-ray diffractometer to obtain a third spectrum, and the third spectrum is compared with the standard spectrum;

[0020] calculating a second difference between each peak in the third spectrum and a peak corresponding to each peak in the standard spectrum;

[0021] When it is determined that the second difference is within the second preset range, it indicates that the incompleteness of the metal organic framework produced by the synthesis reagent is within the second set range, and the first preset condition for producing the synthesis reagent is changed.

[0022] Furthermore, the preparation method also includes:

[0023] When it is determined that the second difference is not within the second preset range, the ratio of the synthetic reagents is changed.

[0024] Furthermore, the liquid mixture includes ionic liquid and amine solution.

[0025] Further, the volume fraction of the liquid mixture is 0% to 10% of the initial skeleton structure powder.

[0026] Further, the preset conditions include that during the mixing process, the temperature is 80° C. to 120° C., and DMF or ethanol is used as the organic solvent.

[0027] Further, the preset temperature is 80°C to 100°C.

[0028] When applying the technical solution of the present invention, it is necessary to obtain the characteristic information of the original metal organic skeleton during use, and construct an initial skeleton structure based on the characteristic information. After the initial skeleton structure is constructed, the composition of the synthesis reagent is determined based on the material of the preset skeleton. After the composition of the synthesis reagent is determined, it is necessary to obtain a liquid mixture, and under preset conditions, the liquid mixture is mixed with the synthesis reagent to obtain a mixed liquid, and the obtained mixed liquid is mixed with the initial skeleton structure, and dried at a preset temperature. After drying, a metal organic skeleton is obtained. The metal organic skeleton produced by the method of the present application can not only maintain structural stability, but also can further increase the adsorption capacity of carbon dioxide compared with the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0030] Figure 1 A schematic diagram of making a metal organic framework according to the present invention is shown. DETAILED DESCRIPTION

[0031] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0033] Unless otherwise specifically stated, the relative arrangement, numerical expressions and numerical values ​​of the parts and steps set forth in these embodiments do not limit the scope of the present invention. Meanwhile, it should be understood that, for ease of description, the sizes of the various parts shown in the accompanying drawings are not drawn according to the actual proportional relationship. The technology, method and equipment known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the technology, method and equipment should be considered as a part of the specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary, rather than as a limitation. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar reference numerals and letters represent similar items in the following drawings, and therefore, once a certain item is defined in an accompanying drawing, it does not need to be further discussed in subsequent drawings.

[0034] In the prior art, carbon dioxide is adsorbed mainly through the structure of a metal organic framework, but the adsorption capacity of the metal organic framework structure is limited. The metal organic framework is a porous material with a regular pore structure that can selectively adsorb or exclude molecules according to the size of the molecules.

[0035] Therefore, the purpose of this application is to provide a method for preparing a metal organic framework in view of the above problems. The preparation method comprises:

[0036] S1. Acquire characteristic information of the original metal organic framework, and construct an initial framework structure according to the characteristic information, wherein the characteristic information includes the number of atoms in the original metal organic framework, the size of the pores, and the length of the pores;

[0037] Specifically, Figure 1 As shown, the characteristic information of the original metal organic framework is obtained, and the characteristic information includes the number of atoms in the original metal organic framework, the size of the pore size and the length of the pore. After obtaining the characteristic information, the initial skeleton structure is first constructed using the Material Studio software, and a three-dimensional structure model is made based on the initial skeleton structure. The specific production process is as follows:

[0038] Place a carbon dioxide molecule at any site on each pore, and calculate the binding energy of the carbon dioxide molecule at each site based on density functional theory. According to the calculation results of the binding energy, find the site with the lowest binding energy, because the structure at the site with the lowest binding energy is the most stable. The formula for calculating the binding energy of the carbon dioxide molecule at each site is:

[0039] BE=E optim(有机金属骨架+气体分子) -E optim(气体分子) -E optim(有机金属骨架)

[0040] E optim(有机金属骨架+气体分子)Represents the total energy of gas molecules adsorbed on the organic metal framework

[0041] E optim(气体分子) Represents the total energy of the gas molecules

[0042] E optim(有机金属骨架) Represents the total energy of the metal organic framework

[0043] The actual metal organic framework is made according to the number of atoms in the three-dimensional model structure.

[0044] During use, it is necessary to obtain the characteristic information of the original metal organic skeleton and construct an initial skeleton structure based on the characteristic information. After the initial skeleton structure is constructed, the composition of the synthesis reagent is determined based on the preset skeleton material. After the composition of the synthesis reagent is determined, it is necessary to obtain a liquid mixture, and under preset conditions, mix the liquid mixture with the synthesis reagent to obtain a mixed liquid. The obtained mixed liquid is mixed with the initial skeleton structure and dried at a preset temperature. After drying, a metal organic skeleton is obtained. The metal organic skeleton produced by the method of the present application can not only maintain structural stability, but also can further increase the adsorption capacity of carbon dioxide compared to the prior art.

[0045] S2. Determine the composition of the synthetic reagent according to the material of the preset skeleton;

[0046] irradiating the synthesis reagent with an X-ray diffractometer to obtain a first spectrum;

[0047] Acquire a standard spectrum, and calculate a first difference between each peak in the first spectrum and a corresponding peak in the standard spectrum;

[0048] When it is determined that the first difference is within a first preset range, it indicates that the metal organic framework structure produced according to the synthesis reagent is complete;

[0049] When it is determined that the first difference is not within the first preset range, it indicates that the metal organic framework structure produced according to the synthesis reagent is incomplete;

[0050] irradiating the synthesis reagent with a scanning electron microscope to obtain a second spectrum, wherein the second spectrum is used to characterize the degree of incompleteness of the metal organic framework produced by the synthesis reagent;

[0051] When it is determined that the degree of incompleteness is within a first set range, a first preset condition for preparing the synthetic reagent is changed, wherein the first preset condition includes temperature, pressure and time;

[0052] When the degree of incompleteness is judged to be outside the first set range, the synthesis reagent is irradiated with an X-ray diffractometer to obtain a third spectrum, and the third spectrum is compared with the standard spectrum;

[0053] calculating a second difference between each peak in the third spectrum and a peak corresponding to each peak in the standard spectrum;

[0054] When it is determined that the second difference is within the second preset range, it indicates that the incompleteness of the metal organic framework produced by the synthesis reagent is within the second set range, and the first preset condition for producing the synthesis reagent is changed;

[0055] When it is determined that the second difference is not within the second preset range, the ratio of the synthetic reagents is changed.

[0056] Specifically, the composition of the synthesis reagent is determined according to the material of the preset skeleton. For example, if the material of the preset skeleton is zinc, it is necessary to make the corresponding composition of the synthesis reagent based on zinc, and finally determine the composition of the synthesis reagent. Because the actual metal-organic skeleton is produced through the synthesis reagent, after the composition of the synthesis reagent is determined, it is necessary to judge the structural stability of the synthesis reagent.

[0057] First, the synthesis reagent is irradiated by an X-ray diffractometer to obtain a first spectrum, and a standard card is obtained. The standard card refers to a card obtained by irradiating the synthesis reagent with an X-ray diffractometer when the structure is in a stable state. The first difference between each peak in the first spectrum and the corresponding peak on the standard card is calculated. When it is determined that the first difference is within a first preset range, it indicates that the structure of the metal organic framework produced according to the current synthesis reagent composition is in a stable state.

[0058] When it is determined that the first difference is not within the first preset range, it indicates that the structure of the metal organic framework produced according to the current synthesis reagent is incomplete. At this time, it is necessary to use a scanning electron microscope to irradiate the synthesis reagent and obtain a second spectrum. The second spectrum can be used to characterize the degree of incompleteness of the metal organic framework produced using the synthesis reagent. If the structure of the metal organic framework can be intuitively seen in the second spectrum, that is, the degree of incompleteness of the metal organic framework is within the first set range, then it is necessary to change the first preset condition for producing the synthesis reagent;

[0059] Among them, the first preset condition is the temperature, pressure and time when the synthetic reagent is prepared. When it is judged that the degree of incompleteness is outside the first set range, the synthetic reagent is irradiated with an X-ray diffractometer to obtain a third spectrum, and then the third spectrum is compared with the standard spectrum, and the second difference between each peak in the third spectrum and the corresponding peak in the standard spectrum is calculated. When it is judged that the second difference is within the second preset range, it is necessary to change the first preset condition when preparing the synthetic reagent. If it is judged that the second difference is not within the second preset range, it is necessary to readjust the ratio of the synthetic reagent.

[0060] S3, obtaining a liquid mixture, and mixing the liquid mixture with a synthetic reagent under preset conditions to obtain a mixed solution;

[0061] The liquid mixture includes an ionic liquid and an amine solution, and the volume fraction of the liquid mixture is 0% to 10% of the initial skeleton structure powder. The preset conditions include that during the mixing process, the temperature is 80° C. to 120° C., and DMF or ethanol is used as the organic solvent.

[0062] Specifically, after the composition of the synthetic reagent is determined, a liquid mixture needs to be obtained, wherein the liquid mixture includes an ionic liquid and an amine solution, and the volume fraction of the liquid mixture is 0% to 10% of the initial skeleton structure powder state. The obtained liquid mixture is mixed with the synthetic reagent to obtain a mixed liquid. The preset condition means that during the mixing process of the two, the temperature is between 80°C and 120°C, and DMF or ethanol is used as the organic solvent for mixing.

[0063] S4. Mixing the mixed liquid with the initial framework structure and drying it at a preset temperature to obtain a metal organic framework.

[0064] The preset temperature is 80℃ to 100℃.

[0065] Specifically, after the mixed liquid is mixed with the initial framework structure, it is dried at a preset temperature to obtain a metal organic framework, wherein the preset temperature is 80°C to 100°C.

[0066] From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: the metal organic framework produced by the method of the present application can not only maintain structural stability, but also can further increase the adsorption capacity of carbon dioxide compared with the prior art.

[0067] In the description of the present invention, it is necessary to understand that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "lateral, vertical, perpendicular, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the devices or elements referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention. The directional words "inside and outside" refer to the inside and outside relative to the contours of each component itself.

[0068] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used here to describe the spatial positional relationship between a device or feature and other devices or features as shown in the figure. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figure. For example, if the device in the accompanying drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below other devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0069] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. If not otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0070] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a metal organic framework, characterized in that: include: Acquiring characteristic information of the original metal organic framework, and constructing an initial framework structure according to the characteristic information, wherein the characteristic information includes the number of atoms in the original metal organic framework, the size of the pores, and the length of the pores; Determine the composition of the synthetic reagent according to the material of the preset skeleton; Obtaining a liquid mixture, and mixing the liquid mixture with the synthetic reagent under preset conditions to obtain a mixed solution; The mixed liquid is mixed with the initial framework structure, and dried at a preset temperature to obtain a metal organic framework.

2. The method for preparing a metal organic framework according to claim 1, characterized in that: The step of obtaining the liquid mixture also includes: irradiating the synthesis reagent with an X-ray diffractometer to obtain a first spectrum; Acquire a standard spectrum, and calculate a first difference between each peak in the first spectrum and a corresponding peak in the standard spectrum; When it is determined that the first difference is within the first preset range, it indicates that the metal organic framework structure produced according to the synthesis reagent is complete.

3. The method for preparing a metal organic framework according to claim 2, characterized in that: The production method further comprises: When it is determined that the first difference is not within the first preset range, it indicates that the metal organic framework structure produced according to the synthesis reagent is incomplete.

4. The method for preparing a metal organic framework according to claim 3, characterized in that: After the step of determining that the first difference is not within the first preset range, the following step further includes: irradiating the synthesis reagent with a scanning electron microscope to obtain a second spectrum, wherein the second spectrum is used to characterize the degree of incompleteness of the metal organic framework produced using the synthesis reagent; When it is determined that the degree of incompleteness is within a first set range, the first preset condition for preparing the synthetic reagent is changed, and the first preset condition includes temperature, pressure and time.

5. The method for preparing a metal organic framework according to claim 4, characterized in that: The production method further comprises: When the degree of incompleteness is judged to be outside the first set range, the synthesis reagent is irradiated with an X-ray diffractometer to obtain a third spectrum, and the third spectrum is compared with the standard spectrum; Calculating a second difference between each peak in the third spectrum and a peak corresponding to each peak in the standard spectrum; When it is determined that the second difference is within the second preset range, it indicates that the incompleteness of the metal organic framework produced by the synthesis reagent is within the second set range, and the first preset condition for producing the synthesis reagent is changed.

6. The method for preparing a metal organic framework according to claim 5, characterized in that: The production method further comprises: When it is determined that the second difference is not within the second preset range, the ratio of the synthetic reagent is changed.

7. The method for preparing a metal organic framework according to claim 1, characterized in that: The liquid mixture includes an ionic liquid and an amine solution.

8. The method for preparing a metal organic framework according to claim 1, characterized in that: The volume fraction of the liquid mixture is 0% to 10% of the initial skeleton structure powder.

9. The method for preparing a metal organic framework according to claim 1, characterized in that: The preset conditions include that during the mixing process, the temperature is 80° C. to 120° C., and DMF or ethanol is used as the organic solvent.

10. The method for preparing a metal organic framework according to claim 1, characterized in that: The preset temperature is 80°C to 100°C.

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