CN108704491B - Method for preparing layered metal organic framework film by vapor gel method - Google Patents
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Abstract
The invention relates to a method for preparing a layered metal organic framework film by a vapor gel method, which adopts a dipping-pulling method, firstly introduces a layer of sol-gel layer for providing a metal source on the surface of a carrier to obtain the carrier with a positioning active point of the layered metal organic framework film, directly places the carrier in a solvent-free reaction kettle containing a certain amount of pure organic ligand substances corresponding to the metal organic framework material, and heats the organic ligand in the kettle to form vapor under the condition of certain temperature and no solvent, so as to generate a matching reaction with the metal source gel layer on the surface of the carrier to obtain the continuous and uniform layered metal organic framework film. The method adopted by the invention has the advantages of simple preparation process, environment-friendly preparation without organic solvent, convenience for scale up and enlargement, capability of solving the problems of difficulty and complexity in the preparation of the traditional lamellar metal organic framework film and wide application prospect.
Description
Technical Field
The invention relates to a method for preparing a layered metal organic framework film by a vapor gel method.
Background
In recent years, with the aggravation of energy shortage and the increasing environmental protection awareness of people, compared with the traditional high-energy-consumption and high-pollution separation technology, the membrane separation technology has the obvious advantages of low energy consumption, high separation efficiency, easiness in realizing continuous separation, low carbon emission and the like, and is widely applied to the fields of gas separation, seawater desalination, pervaporation, water pollution treatment and the like. Among them, the performance of a gas separation membrane is always limited by the interplay of permeation flux and selectivity, i.e., the robinson upper limit, due to the "trade-off" effect.
The molecular sieve nanosheet is used as an ideal gas separation membrane construction material, and how to prepare the nanosheet molecular sieve membrane with large area and thin thickness is the key point for breaking through the limitation of the mutual influence of permeation flux and selectivity. However, the preparation of a nanosheet molecular sieve membrane with a large area and high separation performance at the present stage has a great challenge.
Tsiapst topic group mixes polymer and MFI molecular sieve, nanometer molecular sieve nanometer sheet is obtained based on stripping, and molecular sieve membrane constructed by nanometer sheet has certain separation performance of ortho-xylene and para-xylene [ Varoon K, Zhang X, Elyassi B, et al. However, only more than ten kinds of two-dimensional zeolite molecular sieve materials have been discovered so far, and the layered molecular sieve materials have limitations in the aspects of controllability of a synthesis method, easiness of an open-layer method and the like, and relevant researches have not taken obvious breakthrough.
Metal Organic Framework (MOFs) materials are a class of new porous materials developed in recent years and formed by coordination of metals and organic ligands, and have a topology structure similar to that of zeolite molecular sieves, because the framework structure and pore sizes can be reasonably adjusted between the organic ligands and the inorganic metals, and the surface can also be functionally treated, compared with the traditional zeolite molecular sieves, the metal organic framework materials have richer framework structures and adjustable pore sizes. The two-dimensional layered metal organic framework is a branch of metal organic framework materials, and compared with more than ten two-dimensional zeolite molecular sieves, the diversity and the versatility of the two-dimensional layered metal organic framework provide a rich material library for the molecular sieve nanosheets. The zeolite imidazole skeleton is used as an important branch of a metal organic skeleton, has the characteristics of various pore channel structures of metal organic skeleton materials and easily modified skeleton ligands, and simultaneously has micropores smaller than 0.5nm and excellent chemical stability and thermal stability, and the two-dimensional zeolite imidazole skeleton also has the excellent characteristics. If the layered two-dimensional zeolite imidazole framework can be layered to a nanometer scale, the nano-sheet molecular sieve membrane can be assembled.
In recent years, researchers have paid great attention to how to delaminate a layered metal organic framework and prepare a nanosheet molecular sieve membrane. At present, the preparation of 2D ultrathin nanosheet type separation membranes mainly comprises: the "top-down" and "bottom-up" methods. Recently, Peng et al [ PengY, Li Y, BanY, et al, Metal-Organic Framework semiconductors as building blocks for molecular devices.science, 2014,346:1356-1359.Peng Y, Li Y, BanY, et al, two-dimensional Metal-Organic Framework Nanosheets for Membrane-Based separation. Angewandte chemical International Edition,2017,56:9757 and 9761 ] obtained ultra-thin nano-sheet gas separation membranes using the "top-down" method, peeled off multi-layer zeolite imidazole Framework materials, obtaining ultra-thin films not exceeding 100nm on sheet supports at 200 ℃ and having high gas separation performance. The preparation method also cannot avoid the limitation of a top-down method, namely the preparation process is complex, the conditions are harsh, the time consumption is high, the yield is low, the lamella size is small, the nanosheets are easily damaged by the method, the nanosheets are easily stacked, the gas separation performance is further influenced, the repeatability of preparation of the separation membrane is reduced, and the further development, research and application are not facilitated. The nano-sheets can also be obtained in solution by adopting a "bottom-up" method. Tania et al [ Rodenas T, LuzI, Prieto G, et al, metal-organic framework nanosheets in polymer composites for gas separation. nature Materials,2015,14:48-55 ] prepared ultrathin metal organic framework nanosheets by means of different solvent interfaces and mixed with organic matter to prepare hybrid membranes having better gas separation performance. However, the process needs more organic solvents with high toxicity, the yield of the prepared nanosheets is low, and the permeation flux of the prepared hybrid membrane is low. So far, no simple, efficient and environment-friendly technology and method for preparing a high-quality layered metal organic framework film exist.
Disclosure of Invention
The invention provides a novel method for preparing a layered metal organic framework film by a vapor gel method, aiming at the problems of complex and difficult preparation, low repeatability and the like of the prior layered metal organic framework film. The preparation method does not need an organic solvent, has the advantages of environmental protection, simple operation process, high yield, large-area film forming and high repeatability, and has good amplification and application prospects.
The invention has the following inventive concept: firstly, introducing a layer of sol-gel layer for providing a metal source on the surface of a carrier by lifting to serve as a positioning active point of a layered metal-organic framework film, and obtaining the carrier with the positioning active point of the layered metal-organic framework film; then the carrier is directly placed in a solvent-free reaction kettle containing a ligand pure substance of the metal organic framework material, the organic ligand in the kettle is directly heated to form steam under the condition of certain temperature and no solvent, and the generated steam is contacted and matched with ions of a metal source gel layer on the surface of the carrier to form a continuous and uniform two-dimensional nano sheet type layered metal organic framework film.
The invention adopts the technical scheme that a layered metal organic framework membrane is prepared by a vapor gel method, zinc or cobalt is used as central ions, benzimidazole is used as an organic ligand to form a zeolite imidazole framework type layered metal organic framework membrane, and a used carrier is a porous alumina ceramic tube or ceramic sheet or non-porous glass sheet type carrier with the average pore diameter of 200 nm-2 mu m.
The invention also aims to protect a preparation method of the layered metal organic framework film by the vapor gel method, which comprises the following steps: s1, introducing a layer of sol-gel layer for providing a metal source in advance on the surface of a carrier to prepare the carrier with a metal gel layer;
s2, suspending the carrier with the metal gel layer in a stainless steel reaction kettle filled with benzimidazole polytetrafluoroethylene, and reacting for 4-12 hours at 180-200 ℃ to obtain the two-dimensional layered metal organic framework membrane.
The metal source gel-sol layer is a zinc sol-gel layer or a cobalt sol-gel layer. According to the lifted gel layers of different metal sources (zinc or cobalt), two-dimensional layered metal-organic framework films of different metal sources (zinc or cobalt) can be obtained correspondingly.
The metal sol solution in the step S1 is prepared by the following method: stirring ethylene glycol monomethyl ether and acetate in a water bath, slowly dropwise adding a certain amount of ethanolamine, and stirring at room temperature to obtain a uniform metal sol solution. More specifically, the molar ratio of ethylene glycol monomethyl ether to acetate is 20:1, the water bath temperature is 70 ℃, and the molar ratio of ethanolamine: acetate is stirred for 24 hours at room temperature to obtain uniform metal sol liquid according to the mol ratio of 2:1, the metal sol liquid is introduced to the surface of the carrier by a pulling or spin coating method, and the carrier with the uniform metal gel layer is obtained after drying for 1 hour at 120 ℃; wherein the acetate is zinc acetate and/or cobalt acetate.
In the method, the metal sol solution is pulled or spin-coated on the surface of the carrier for a certain time, generally 2s-60s, and two-dimensional layered metal-organic framework films with different thicknesses can be obtained according to different coating times in actual production.
In step S2, the benzimidazole added to the stainless steel reaction kettle made of teflon is excessive, and it is required to ensure that the support having the metal gel active layer and the benzimidazole are not contacted.
Compared with the prior art, the invention has the beneficial effects that:
the method for preparing the layered metal organic framework film by the vapor gel method provided by the invention has the advantages of simple preparation process, environment-friendly preparation without organic solvent, high yield, large-area film formation, high repeatability, convenience for scale up and enlargement, capability of solving the problems of difficult and complicated preparation, low repeatability and the like in the preparation process of the traditional lamellar metal organic framework film, and wide application prospect.
Drawings
FIG. 1a is an electron micrograph of the surface of a unloaded body.
FIG. 1b is an electron micrograph of the sol-gel layer modified support surface.
FIG. 2a is an electron microscope image of the surface of a cobalt-based two-dimensional layered metal-organic framework film induced by a cobalt sol-gel layer.
FIG. 2b is an electron microscope image of a cross-section of a cobalt-based two-dimensional layered metal-organic framework film induced by a cobalt sol-gel layer.
Figure 2c is an XRD pattern of the sample synthesized in example 1.
FIG. 3a is an electron microscope image of the zinc-based two-dimensional layered metal-organic framework film surface induced by a zinc sol-gel layer.
FIG. 3b is an electron microscope image of a cross section of a zinc-based two-dimensional layered metal-organic framework film induced by a zinc sol-gel layer.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1 two-dimensional layered Co2(bim)4Preparation of nano-sheet type film
(1) The porous carrier is selected to be a porous alumina ceramic tube with an average pore diameter of about 200 nm. The porous carrier is ultrasonically washed by deionized water and ethanol for a plurality of times before use, then is roasted in a muffle furnace at 400 ℃ for 2 hours, is cooled to room temperature, and is placed in a dryer for standby.
(2) A cobalt sol layer is introduced into the inner surface of the alumina ceramic carrier. 9.3624g of cobalt acetate is added into 50ml of ethylene glycol monomethyl ether, stirred for 0.5h in a water bath at 70 ℃, 4.6ml of ethanolamine is slowly dropped as a stabilizer, and stirred for 24h at room temperature to obtain a uniform cobalt sol solution. And then dip-coating the cobalt sol layer on the inner surface of the alumina ceramic carrier in the step (1) by dip-coating, and drying at 120 ℃ for 1h to obtain the porous carrier with a uniform cobalt gel layer, wherein compared with the porous carrier (shown in a figure 1a), the gel layer can modify obvious defects on the surface of the carrier (shown in a figure 1b) and simultaneously provide uniform metal active sites for preparing the nano sheet type membrane.
(3) Two-dimensional layered Co growing on surface of alumina ceramic carrier2(bim)4A nanosheet membrane. Suspending the porous carrier with the cobalt gel layer in the step (2) in a stainless steel reaction kettle of polytetrafluoroethylene added with benzimidazole to ensure that the carrier with the metal gel active layer can not contact with the benzimidazole, taking out the ceramic tube after reacting for 4-12h at 200 ℃, slowly washing the surface of the membrane layer by methanol, and naturally drying to obtain the layered Co with horizontal oriented growth2(bim)4Nanosheet films (see fig. 2b), X-ray diffraction confirmed that the films produced had a high degree of c-axis orientation (see fig. 2 c).
Example 2 two-dimensional layered Zn2(bim)4Preparation of nano-sheet type film
(1) The porous carrier is selected to be a porous alumina ceramic tube with an average pore diameter of about 200 nm. The treatment procedure was the same as in (1) of example 1;
(2) the inner surface of the alumina ceramic carrier is introduced with a zinc sol layer. 8.2621g of zinc acetate is added into 50ml of ethylene glycol monomethyl ether, stirred for 0.5h in a water bath at 70 ℃, 4.6ml of ethanolamine is slowly dropped as a stabilizer, and stirred for 24h at room temperature to obtain a uniform cobalt sol solution. Then dip-coating the zinc sol layer on the inner surface of the alumina ceramic carrier in the step (1) to form a zinc sol layer, and drying the zinc sol layer for 1 hour at 120 ℃ to obtain a porous carrier with a uniform zinc gel layer;
(3) growing two-dimensional layered Zn on the surface of an alumina ceramic carrier2(bim)4A nanosheet membrane. The same as in step (3) of example 1, except that the porous support having the zinc gel layer in step (2) was suspended in a stainless steel reaction vessel of polytetrafluoroethylene to which benzimidazole was added. As shown in FIG. 3, the layered Zn with horizontally oriented growth can still be obtained by the vapor-gel method2(bim)4A nanosheet membrane.
EXAMPLE 3 two-dimensional layer formation (Zn/Co)2(bim)4Preparation of nano-sheet type film
(1) The porous carrier is selected to be a porous alumina ceramic tube with an average pore diameter of about 200 nm. The treatment procedure was the same as in (1) of example 1;
(2) the inner surface of the alumina ceramic carrier is introduced with a zinc/cobalt mixed sol layer. Adding zinc acetate and cobalt acetate into 50ml of ethylene glycol monomethyl ether, and maintaining the ratio of ethylene glycol methyl ether in the gel liquid: the molar ratio (zinc acetate + cobalt acetate) was 20:1, stirring for 0.5h in a water bath at 70 ℃, slowly dropwise adding 4.6ml of ethanolamine serving as a stabilizer, and stirring for 24h at room temperature to obtain a uniform zinc/cobalt mixed sol solution. Then dipping, pulling and coating the porous carrier on the inner surface of the alumina ceramic carrier in the step (1) to form a zinc-cobalt sol layer, and drying at 120 ℃ for 1h to obtain the porous carrier with a uniform zinc/cobalt gel layer;
(3) growing two-dimensional layer (Zn/Co) on the surface of the alumina ceramic carrier2(bim)4A nanosheet membrane. The same as in step (3) of example 1, except that the porous support having the zinc/cobalt gel layer in step (2) was suspended in a stainless steel reaction vessel of polytetrafluoroethylene with benzimidazole added.
EXAMPLE 4 two-dimensional layered (Co)2(bim)4Gas permeability testing of nanosheet membranes
Two-dimensional layered structure (Co) prepared by the example of the present invention2(bim)4The flux of single component gas and the change of the rational gas separation selectivity of the nano sheet type membrane along with the aerodynamic diameter are tested by the nano sheet type membrane at 30 ℃ and 0.1 MPa: the flux of hydrogen was 17.2X 10-8mol m-2s-1Pa-1，H2/CO2、H2/N2、H2/CH4The ideal separation coefficients of (a) are 58.7, 49.7, 68.6 respectively. Illustrating the two-dimensional layered structure (Co) prepared by the vapor-gel method2(bim)4The nano-sheet type membrane has excellent separation effect on gas.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (7)
1. A method for preparing a layered metal organic framework membrane by a vapor gel method is characterized in that a zeolite imidazole framework layered metal organic framework membrane is formed by taking zinc or cobalt as a central ion and benzimidazole as an organic ligand, a carrier used is a porous alumina ceramic tube or ceramic wafer with the average pore diameter of 200 nm-2 mu m, and the method specifically comprises the following steps:
s1, introducing a layer of sol-gel layer for providing a metal source in advance on the surface of a carrier to prepare the carrier with a metal gel layer;
s2, suspending the carrier with the metal gel layer in a stainless steel reaction kettle filled with benzimidazole polytetrafluoroethylene, and reacting for 4-12 hours at 180-200 ℃ to obtain the two-dimensional layered metal organic framework membrane.
2. The method of claim 1, wherein the metal source gel-sol layer is a zinc sol-gel layer or a cobalt sol-gel layer.
3. The method according to claim 1, wherein the metal sol solution in step S1 is prepared by the following method: stirring ethylene glycol monomethyl ether and acetate in a water bath, slowly dropwise adding a certain amount of ethanolamine, and stirring at room temperature to obtain a uniform metal sol solution.
4. The method according to claim 3, wherein the step S1 is specifically: stirring ethylene glycol monomethyl ether and acetate at a molar ratio of 20:1 in a 70 ℃ water bath, and slowly dropwise adding a certain amount of ethanolamine, ethanolamine: acetate is stirred for 24 hours at room temperature to obtain uniform metal sol liquid according to the mol ratio of 2:1, the metal sol liquid is introduced to the surface of the carrier by a pulling or spin coating method, and the carrier with the uniform metal gel layer is obtained after drying for 1 hour at 120 ℃; wherein the acetate is zinc acetate or cobalt acetate.
5. The method as claimed in claim 1, wherein the two-dimensional layered metal-organic framework films with different thicknesses are obtained according to the time of coating the metal sol solution on the surface of the carrier in the pulling or spin coating time.
6. A method according to claim 4, wherein the metal sol solution is pulled or spun onto the surface of the support for a period of time in the range of 2s to 60 s.
7. The method of claim 1, wherein in step S2, an excess amount of benzimidazole is added to a stainless steel reaction kettle made of polytetrafluoroethylene.
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