CN112657351B - Method for preparing high-orientation MOF nano-sheet membrane by utilizing self-rotation of layered metal hydroxide - Google Patents
Method for preparing high-orientation MOF nano-sheet membrane by utilizing self-rotation of layered metal hydroxide Download PDFInfo
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Abstract
The invention belongs to the field of MOF nano-sheet membrane preparation, and discloses a method for preparing a high-orientation MOF nano-sheet membrane by utilizing self-transformation of layered metal hydroxide. Firstly, introducing a thin layer of two-dimensional Co (OH) on the surface of a carrier2Nanosheet layer, then self-transformation to obtain highly oriented Co2(bIm)4A nanosheet membrane. Two dimensional Co (OH)2The nano sheet has a two-dimensional ultrathin structure, can be flatly laid on the surface of a carrier, and is greatly favorable for controlling the oriented growth of a two-dimensional film under the condition of not adding any external force assistance, so that Co can be dissociated in a ligand synthetic solution containing a structure regulator2+And further combined with a ligand to generate highly oriented Co2(bIm)4A nanosheet membrane. The simple preparation method can be extended to the preparation of other two-dimensional films, and opens up a new way for preparing highly oriented ultrathin two-dimensional nano MOF films.
Description
Technical Field
The invention belongs to the field of MOF nano-sheet membrane preparation, and relates to a method for preparing a high-orientation MOF nano-sheet membrane by utilizing self-transformation of layered metal hydroxide. Provides a new way for preparing the high-orientation MOF nano-sheet type membrane.
Background
The separation of the mixture is crucial in the chemical industry, but the energy consumption of the separation process accounts for more than 40% of the whole industrial energy. Compared with the traditional separation technology, membrane separation has attracted extensive attention due to the characteristics of higher separation effect, low energy consumption, environmental friendliness and the like, but the permeability and selectivity of the membrane are generally mutually restricted, namely limited by the upper Robertson limit. However, the development of high permeability and high selectivity membrane layers is limited by the limitations of conventional membrane materials and the limitations of the membrane fabrication process.
In recent years, the advantages of ultrathin two-dimensional materials with the thickness of only one to a few atoms are gradually shown and the research level is continuously improved, and the two-dimensional materials with high selectivity and high flux are rapidly becoming ideal materials for preparing high-performance separation membranes, and show extraordinary separation performance in various membrane separation processes such as ultrafiltration, nanofiltration, reverse osmosis, pervaporation, gas separation and the like. Unlike conventional three-dimensional membrane materials, separation membranes designed from two-dimensional materials have ultra-thin characteristics, and can achieve minimum transport resistance and maximum permeation flux. By reasonably adjusting and accurately controlling the interlayer distance and the nano-aperture of the two-dimensional material, liquid, gas, ions and other species can selectively and quickly pass through the two-dimensional material, so that high-performance separation is realized. Therefore, the ultrathin two-dimensional porous nanosheet type membrane has ultrahigh permeability and excellent selectivity, is expected to break through the Robertson upper limit, is an ideal structure of a separation membrane, and is the most promising and challenging research subject in the field of membrane separation in the future.
At present, the research on two-dimensional membrane materials mainly focuses on graphene and graphene oxide, MXene materials, layered double hydroxides, zeolite molecular sieve nanosheets, metal-organic framework nanosheets and the like, and the obtained two-dimensional structural separation membrane has a prominent application value in the separation field. For example, professor King of Nanjing university of industry and his coworkers can simply and precisely control the distance between graphene oxide layers by adding specific cations, and achieve excellent ion interception rate [ Chen L, Shi G, Shen J, et al].Nature,2017,550(7676):380-383]. The two-dimensional MXene separation membrane also has excellent water permeability and separation performance, such as Ti prepared by etching and ultrasonic action reported by professor Wang Haihui of south China university3C2TXThe nano-sheet is assembled on a porous carrier to prepare a two-dimensional MXene separation membrane, which has excellent water permeability and higher molecular interception rate and has practical application value in the field of water purification [ Li H, Song Z, Zhang X, et al].Science,2013,342(6154):95-98]. In addition, the subject group applies two-dimensional MXene separation membrane to gas separation in hydrogen gasPermeability and H2/CO2Exhibits excellent performance in terms of separation selectivity [ Li L, Zhang T, Duan Y, et al].Journal of Materials Chemistry A,2018,6(25):11734-11742]. The TsAtisis subject group of the university of Minnesota in America firstly peels a layered zeolite molecular sieve precursor to successfully prepare a molecular sieve nanosheet dispersion liquid with perfect crystallinity, assembles and prepares an ultrathin two-dimensional MFI zeolite molecular sieve membrane by a simple filtering, depositing and assembling technology and is applied to the separation of xylene isomers, and the separation performance of the ultrathin two-dimensional MFI zeolite molecular sieve membrane is far higher than that of a conventional zeolite molecular sieve membrane [ Varoon K, Zhang X, Elyassi B, et al].Science,2011,334(6052):72-75]. Aiming at the research of a two-dimensional MOF crystal separation membrane, Yangweicau et al, the institute of chemical and physical research, in the presence of a methanol/n-propanol mixed solvent2(bIm)4Performing wet ball milling stripping, preparing a two-dimensional ultrathin MOF molecular sieve separation membrane with the thickness of about 5nm by adopting a pulling method, and applying the two-dimensional ultrathin MOF molecular sieve separation membrane to the separation of mixed gas, wherein the separation performance of the two-dimensional ultrathin MOF molecular sieve separation membrane is far higher than that of a reported conventional MOF separation membrane [ Peng Y, Li Y, Ban Y, et al].Science,2014,346(6215):1356-1359]. The previous stage of our research group adopts homologous zinc oxide nano-particle layer to induce and prepare ZIF nano-sheet film [ Li Y, Liu H, Wang H, et al. GO-guided direction growth of high purity oriented metal-organic frame nano-sheets for H2/CO2 separation[J].Chemical Science,2018,9(17):4132-4141]。
In summary, the two-dimensional nanomaterial has the excellent characteristics of large specific surface area, uniform pore structure in size, chemical adjustability and the like, and the assembled two-dimensional nanosheet type separation membrane has excellent separation performance. The key to preparing high-performance two-dimensional separation membranes is the preparation of high-quality two-dimensional materials and an effective method for converting the high-quality two-dimensional materials into two-dimensional membranes, which relate to the problems of formation mechanisms, assembly strategies and the like, and related researches are very critical and very challenging.
Disclosure of Invention
Aiming at overcoming the defects of the prior art and solving the problem of difficulty in preparation of the high-quality two-dimensional cobalt-based MOF separation membrane, the invention provides a method for preparing a high-orientation cobalt-based MOF nanosheet type membrane by in-situ conversion of an orientation cobalt metal hydroxide lamella. The invention firstly introduces a thin two-dimensional Co (OH) layer on the surface of a porous carrier by a pulling technology or a rotary coating method2Obtaining a carrier with a two-dimensional metal active layer; then the carrier with the two-dimensional metal active layer is placed in an organic ligand synthetic fluid containing a structure regulator to be converted into highly-oriented two-dimensional Co2(bIm)4A nanosheet membrane. Co (OH) incorporation by control of support surface2The thickness of the nano-sheet layer can be accurately regulated and controlled to prepare two-dimensional Co2(bIm)4Thickness of the nanosheet film. The synthesis method has the advantages of simple operation, high film preparation repeatability, large-area film formation and the like, solves the preparation difficulty of the current high-performance two-dimensional separation film, particularly solves the bottleneck problem of preparing a cobalt-based two-dimensional film, and has potential and huge application prospect.
The above purpose of the invention is realized by the following technical scheme:
the high-orientation MOF nano-sheet membrane is a ZIF structure type formed by coordination with cobalt as a metal center and benzimidazole as an organic ligand. The porous carrier is a porous ceramic tube or ceramic chip with the average pore diameter of 200 nm-2 μm, and the method comprises the following steps:
step (1): first, Co (OH) is prepared2Nano-sheets, dispersing the nano-sheets into a methanol solution, and finally introducing Co (OH) on the surface of the carrier by adopting a pulling or spin coating method2And a nano-sheet layer for preparing the carrier with the metal active layer.
Step (2): vertically suspending a carrier with a metal active layer in an MOF (metal organic framework) film layer synthetic liquid, and performing in-situ self-transformation to form highly-oriented two-dimensional Co2(bIm)4A nanosheet membrane.
Further, the step (1) isPreparation of Co (OH)2The nano sheet is specifically as follows: mixing cobalt acetate: deionized water: hydrazine hydrate: ammonia water according to a molar ratio of 1: 2000-5000: 1-3: 10-30, heating and refluxing for 1-5 h at 80-95 ℃, and finally centrifugally washing for 3 times by using deionized water to obtain Co (OH)2Nanosheets.
Further, the step (1) is specifically as follows: co (OH)2Dispersing the nano sheets in a methanol solution to obtain Co (OH) with the mass fraction of 0.1-5%2Methanol solution, and Co (OH) prepared by using a pulling technique or a spin coating method2Introducing methanol solution onto the surface of the carrier, and drying at 80 deg.C for 2 hr to obtain oriented Co (OH)2A support of the nanosheet layer.
Further, in the step (1), according to different times of lifting and pulling the surface of the carrier or different spin-coating time, Co (OH)2 nanosheet layers with different thicknesses are obtained, so that Co2(bIm)4 nanosheet type film layers with different thicknesses are prepared.
Further, the preparation of the MOF film layer synthetic liquid in the step (2) is mixed according to the following molar ratio: benzimidazole: ammonia water: toluene: methanol 1: 1-4: 10-40: 20 to 100.
Further, Co in the step (2)2(bIm)4The reaction temperature of the nano-sheet type film is 80-150 ℃, the growth time is 6-48 h, and the high-orientation two-dimensional Co is obtained2(bIm)4A nanosheet membrane.
Compared with the prior art, the invention has the beneficial effects that:
the invention introduces a thin layer of two-dimensional Co (OH) on the surface of the carrier2Nanosheet layer, then self-transformation to obtain highly oriented Co2(bIm)4A nanosheet membrane. Two dimensional Co (OH)2The nano sheet has a two-dimensional ultrathin structure, can be flatly laid on the surface of a carrier, and is greatly favorable for controlling the oriented growth of a two-dimensional film under the condition of not adding any external force assistance, so that Co can be dissociated in a ligand synthetic solution containing a structure regulator2+And further combined with a ligand to generate highly oriented Co2(bIm)4A nanosheet membrane. Two dimensional Co (OH)2Orientation of nanosheet layer as a nanosheet filmGrowth provides a good anchor site and metal source. Furthermore, by controlling the introduction of Co (OH) into the surface of the support2The thickness of the nanosheet layer can be accurately regulated and controlled to prepare Co2(bIm)4Thickness of the nanosheet membrane. Co based on preparation2(bIm)4The ultrathin structure and high orientation of the nanosheet membrane can exhibit excellent gas separation capability. The simple preparation method can be expanded to the preparation of other two-dimensional films, and a new way for preparing the highly-oriented ultrathin two-dimensional nano MOF film is opened up.
Drawings
FIG. 1 shows a carrier coated with Co (OH)2SEM image of nanosheets.
FIG. 2 shows Co prepared in example 12(bIm)4SEM images of nanosheet membranes; (a) is a surface SEM image, and (b) is a cross-sectional SEM image.
FIG. 3 shows Co prepared in example 22(bIm)4And (4) a cross section SEM image of the nanosheet type membrane.
FIG. 4 is prepared Co (OH)2XRD spectrum of nanosheet.
FIG. 5 shows the prepared Co2(bIm)4XRD spectrogram of the nano-sheet type film.
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
A method for preparing a high-orientation cobalt-based MOF nano sheet membrane by utilizing in-situ conversion of an orientation cobalt metal hydroxide sheet layer;
step (1): selecting an alumina porous ceramic tube or a porous ceramic plate with the average pore diameter of 200nm as a carrier, respectively ultrasonically cleaning with deionized water and absolute ethyl alcohol for 30min before use to remove impurities, and drying in a vacuum oven at 60 ℃ for 3 h.
Step (2): a250 mL round bottom flask was charged with 0.6225g of tetrahydrate and cobalt acetate, 200mL of deionized water, 175 μ L of hydrazine hydrate (85%) and 5mL of ammoniaHeating and refluxing for 1.5h at 95 deg.C, cooling the resultant to room temperature, centrifuging with deionized water for 3 times to obtain Co (OH)2Nanosheets.
And (3): mixing Co (OH)2The nanosheets are dispersed in a methanol solution to prepare Co (OH) with the mass fraction of 2%2And (4) carrying out ultrasonic treatment on the methanol solution for 30min to uniformly disperse the methanol solution. Then pulling and coating the surface of the carrier in the step (1) for 2 times, wherein the single pulling time is 20s, and drying the carrier in an oven at 80 ℃ for 1h after each pulling is finished to obtain the carrier with Co (OH)2A support for the nanosheet active layer.
And (4): subjecting the product obtained in step (3) to a reaction with Co (OH)2The carrier of the nano-sheet active layer is vertically suspended in the MOF film layer synthetic liquid, and the molar ratio of each component of the synthetic liquid is benzimidazole: ammonia water: toluene: methanol 1: 2: 18: 48, reacting for 10 hours at 100 ℃ in a stainless steel reaction kettle made of polytetrafluoroethylene. Cooling to room temperature after the reaction is finished, taking out the ceramic tube carrier gently, washing the surface of the film layer slowly by using a methanol solution, and then drying in a vacuum oven at 40 ℃ overnight to obtain the Co with high orientation2(bIm)4A nanosheet membrane.
Example 2
A method for preparing a high-orientation cobalt-based MOF nano sheet membrane by utilizing in-situ conversion of an orientation cobalt metal hydroxide sheet layer;
the steps (1) and (2) are the same as in example 1.
And (3): mixing Co (OH)2Nanosheets dispersed in methanol solution to give 4% by mass of Co (OH)2And (4) carrying out ultrasonic treatment on the methanol solution for 30min to uniformly disperse the methanol solution. Then pulling and coating the carrier surface in the step (1), wherein the pulling frequency is 5 times, the single pulling time is 20s, and after each pulling is finished, drying the carrier surface in an oven at 80 ℃ for 1h to obtain the carrier with Co (OH)2A support for the nanosheet active layer.
And (4): subjecting the product obtained in step (3) to a reaction with Co (OH)2The carrier of the nano-sheet active layer is vertically suspended in the MOF film layer synthetic liquid, and the molar ratio of each component of the synthetic liquid is benzimidazole: ammonia water: toluene: methanol 1: 1: 9: 24, in a stainless steel reaction kettle of polytetrafluoroethyleneThe reaction is carried out for 12h at 120 ℃. Cooling to room temperature after the reaction is finished, taking out the ceramic tube carrier gently, washing the surface of the film layer slowly by using a methanol solution, and then drying in a vacuum oven at 40 ℃ overnight to obtain the Co with high orientation2(bIm)4A nanosheet membrane.
Example 3
A method for preparing a high-orientation cobalt-based MOF nano sheet membrane by utilizing in-situ conversion of an orientation cobalt metal hydroxide sheet layer;
the steps (1) and (2) are the same as in example 1.
And (3): mixing Co (OH)2The nanosheets are dispersed in a methanol solution to prepare 0.5% by mass of Co (OH)2And (4) carrying out ultrasonic treatment on the methanol solution for 30min to uniformly disperse the methanol solution. Then prepared Co (OH) by adopting a rotary coating method2Introducing a methanol solution to the surface of the carrier, wherein the volume of the spin coating solution is 2mL, the rotating speed is 2000r/min, and after the spin coating is finished, drying the carrier in an oven at 80 ℃ for 1h to obtain a product containing Co (OH)2A support for the nanosheet active layer.
And (4): the compound having Co (OH) obtained in the step (3)2The carrier of the nano-sheet active layer is vertically suspended in the MOF film layer synthetic liquid, and the molar ratio of each component of the synthetic liquid is benzimidazole: ammonia water: toluene: methanol 1: 2: 18: 48, reacting for 12 hours at 120 ℃ in a stainless steel reaction kettle made of polytetrafluoroethylene. Cooling to room temperature after the reaction is finished, taking out the ceramic tube carrier gently, washing the surface of the film layer slowly by using a methanol solution, and then drying in a vacuum oven at 40 ℃ overnight to obtain the Co with high orientation2(bIm)4A nanosheet membrane.
For the highly oriented Co of example 2 prepared by the present invention2(bIm)4The nano-sheet type membrane is subjected to an ideal gas separation test at 30 ℃ and 0.1MPa, wherein H is2/CO2、H2/N2、H2/CH4The ideal separation coefficients of 28.2, 19.6 and 34.5 respectively show that the highly oriented Co2(bIm)4The nano-sheet type membrane has excellent gas separation performance.
The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (6)
1. A method for preparing a high-orientation MOF nanosheet type membrane by utilizing self-transformation of layered metal hydroxide is characterized by comprising the following specific steps of:
step (1): first, Co (OH) is prepared2Nano-sheets, dispersing the nano-sheets into a methanol solution, and finally introducing Co (OH) on the surface of a carrier by adopting a pulling or spin coating method2A nanosheet layer, preparing a support having a metal active layer;
step (2): vertically suspending a carrier with a metal active layer in an MOF (metal organic framework) film layer synthetic liquid, and performing in-situ self-transformation to form highly-oriented two-dimensional Co2(bi m)4A nanosheet membrane.
2. The method of claim 1, wherein Co (OH) in step (1)2The preparation method of the nano sheet comprises the following steps: mixing cobalt acetate: deionized water: hydrazine hydrate: ammonia water according to a molar ratio of 1: 2000-5000: 1-3: 10-30, heating and refluxing for 1-5 h at 80-95 ℃, and finally centrifugally washing for 3 times by using deionized water to obtain Co (OH)2Nanosheets.
3. The method according to claim 1, wherein step (1) is specifically: co (OH)2Dispersing the nano-sheets in a methanol solution to obtain Co (OH) with the mass fraction of 0.1-5%2Methanol solution, and Co (OH) prepared by using a pulling technique or a spin coating method2Introducing methanol solution onto the surface of the carrier, and drying at 80 deg.C for 2 hr to obtain oriented Co (OH)2A support of nanosheets.
4. The method of claim 1, wherein the number of carrier surface pulls in step (1) is based on the number of carrier surface pullsDifferent thicknesses of Co (OH) can be obtained according to different spin coating time2Nanosheet layer to produce Co having different thicknesses2(bi m)4A nano-sheet film layer.
5. The method of claim 1, wherein the film-layer composition solution in step (2) is prepared by mixing the following components in the following molar ratio: benzimidazole: ammonia water: toluene: methanol 1: 1-4: 10-40: 20 to 100.
6. The method of claim 1, wherein Co is used in step (2)2(bi m)4The reaction temperature of the nano-sheet type film is 80-150 ℃, the growth time is 6-48 h, and the high-orientation two-dimensional Co is obtained2(bi m)4A nanosheet membrane.
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