CN113321815B - MOF material with phospholipid bilayer grafted on surface, preparation method and application - Google Patents

MOF material with phospholipid bilayer grafted on surface, preparation method and application Download PDF

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CN113321815B
CN113321815B CN202110705856.9A CN202110705856A CN113321815B CN 113321815 B CN113321815 B CN 113321815B CN 202110705856 A CN202110705856 A CN 202110705856A CN 113321815 B CN113321815 B CN 113321815B
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mof material
lecithin
mof
phosphonic acid
olc
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CN113321815A (en
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仲崇立
孙玉绣
耿晨旭
乔志华
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Zhongheng New Material Technology Shandong Co ltd
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Tianjin Polytechnic University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702

Abstract

The application discloses an MOF material with a surface grafted with a phosphine bilayer, a preparation method and an application thereof, belonging to the technical field of membrane separation. The MOF material with the surface grafted with the phosphine bilayer is characterized in that the surface of a parent MOF material is grafted with the phosphine bilayer consisting of n-octadecyl phosphonic acid-cholesterol-lecithin; the parent MOF material is ZIF-8, ZIF-67, ZIF-71, ZIF-90, MOF-808 or CuBTC. The preparation method comprises the steps of OPA-MOF preparation, OLC-MOF preparation and the like, and the OLC-MOF material is finally obtained and is used as a filler and a polymer to obtain the OLC-MOF material with good C property by ultraviolet irradiation under the action of a photoinitiator3H6Penetration Rate and C3H6/C3H8Optionally C3H6/C3H8Mixed matrix membranes for separation.

Description

MOF material with phospholipid bilayer grafted on surface, preparation method and application
Technical Field
The application belongs to the technical field of membrane separation, and particularly relates to an MOF material with a phospholipid bilayer grafted on the surface, and a preparation method and application thereof.
Background
Olefins play an important role in the chemical industry. For example, propylene is an intermediate for the synthesis of important chemicals such as propylene oxide, acrolein, acrylic acid, and polypropylene. In the petrochemical production processes such as thermal cracking, catalytic cracking, propane dehydrogenation and the like, a large amount of gas mixture of olefin/alkane is generated, and efficient separation and purification technology is required for recovery and utilization.
Because of similar chemical and physical properties of olefin/alkane, the boiling points and the sizes of the olefin/alkane are very close, and the olefin/alkane separation is always a high energy-consuming process in the petrochemical industry. Current separation techniques include cryogenic distillation, pressure swing adsorption, lean oil absorption, etc., which are generally poor in selectivity, low in separation efficiency, and high in energy consumption. Therefore, a new energy-saving separation technology is urgently needed to improve the separation efficiency and reduce the energy consumption and the cost.
Membrane separation processes have become a focus and focus of current research in the field of gas separation because of their high efficiency, low cost and low energy consumption. Mixed matrix membranes are a general term for membranes prepared by uniformly dispersing filler particles in a polymer matrix, and combine the mechanical properties, processability and cost of the polymer with the advantages of filler in terms of permeability and selectivity, thus hopefully breaking the "trade-off" effect that limits polymer membranes. Meanwhile, the maturity of the preparation process of the polymer film avoids the problems of high difficulty, high cost, difficult amplification and the like of a pure crystal film in preparation, and has attracted extensive attention and research.
The metal-organic framework material (hereinafter referred to as MOF material) is a new porous material, and a coordination polymer with a periodic network structure, which is assembled by inorganic metal ions and organic ligands, has the characteristics of high porosity, large specific surface area, adjustable pore size and the like, has wide application prospects in the aspects of gas separation, electrochemistry, catalysis, medicine and the like, and is an ideal material as a mixed matrix membrane filler.
But is currently used for C3H6/C3H8The filler used for preparing the separated mixed matrix membrane generally has poor compatibility between the filler and a polymer, so that the function of the filler cannot be well exerted, and the finally obtained C3H6/C3H8The mixed matrix membrane for separation has the technical problem of gambling between flux and selectivity, namely a 'trade-off' effect.
Disclosure of Invention
In order to solve the technical problems of poor compatibility between the filler and the polymer, the 'trade-off' effect and the like, the application provides an MOF material with a phospholipid bilayer grafted on the surface, a preparation method of the MOF material and a filler prepared from the MOF material3H6/C3H8Use in the preparation of mixed matrix membranes for separation.
Technical principle of the present application
Construction of a porous MOF Material with C3H6/C3H8Table showing the separation effect of a phosphine bilayer (hereinafter abbreviated as OLC) composed of n-octadecyl phosphonic acid (hereinafter abbreviated as OPA) -cholesterol (hereinafter abbreviated as LEC) -lecithin (hereinafter abbreviated as CHO)An MOF material (hereinafter referred to as OLC-MOF material, and referred to as OLC-MOF) with phospholipid bilayers grafted on the surface is dispersed into a polymer film layer, phosphorus atoms P in n-octadecyl phosphonic acid in OLC are bonded with metals in the MOF material to form P-M bonds (wherein M represents metal, P is phosphorus atom in n-octadecyl phosphonic acid), a polymer, namely polyethylene glycol diacrylate (hereinafter referred to as PEGDA), is irradiated by ultraviolet rays of 312nm under the action of a photoinitiator, the polymer undergoes polymerization reaction, and carbonyl groups in a high polymer (hereinafter referred to as PEO) obtained by the polymerization reaction are bonded with phosphate groups in lecithin in OLC, so that a cross-linked network structure is formed between the OLC-MOF material and the PEGDA, and C is formed between OLC and XLPO on the surface of the MOF material3H6/C3H8Gas channel with separation effect to obtain C3H6/C3H8The reaction mechanism of the above-mentioned preparation process is schematically shown in FIG. 1, and the mixed matrix membrane for separation is designated as OLC-MOF/XLPOEO membrane.
Technical scheme of the application
In a first aspect, the application provides an MOF material with a phospholipid bilayer grafted on the surface, and the following technical scheme is adopted: an MOF material with a phospholipid bilayer grafted on the surface, namely a phospholipide bilayer consisting of n-octadecyl phosphonic acid-cholesterol-lecithin is grafted on the surface of a parent MOF material, metal on the parent MOF material and a P atom in n-octadecyl phosphonic acid in the phospholipide bilayer form a P-M bond connection, wherein cholesterol is used as a bridge between the n-octadecyl phosphonic acid and lecithin, and the lecithin layer and the n-octadecyl phosphonic acid are bridged together;
the parent MOF material is ZIF-8, ZIF-67, ZIF-71, ZIF-90, MOF-808 or CuBTC.
The amounts of n-octadecyl phosphonic acid, cholesterol and lecithin used for the above grafting were determined as the parent MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of the lecithin is 1:4-6:4-6: 4-6.
By adopting the technical scheme, the MOF material with the phospholipid bilayer grafted on the surface is grafted on the surfaceThe phosphoric acid group in the lecithin can be bonded and connected with the carbonyl group in the high polymer, so that a cross-linking reaction is carried out between the MOF material with the surface grafted with the phospholipid bilayer and the high polymer to form a network structure, and a p-C pair is formed3H6/C3H8The gas channel with separation effect of 0.40-0.42nm realizes the C-pair3H6/C3H8Separation of (4).
Meanwhile, the phosphate group in the lecithin of the surface of the obtained MOF material with the surface grafted with the phosphine bilayer is bonded with the carbonyl group in the high polymer, so that the MOF material has good compatibility with the raw material for forming the high polymer, namely the polymer, and the technical problem of poor compatibility between the filler and the polymer in the prior art is solved.
Meanwhile, the MOF material with the surface grafted with the phosphine bilayer can be used for preparing the MOF material with good C3H6Penetration rate and C3H6/C3H8Thereby solving the technical problem of the 'trade-off' effect.
Preferably, the amounts of n-octadecyl phosphonic acid, cholesterol and lecithin used for the above grafting are such that the ratio of the parent MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of lecithin is 1: 5: 5: 5.
by adopting the technical scheme, the MOF material with the surface grafted with the phosphine bilayer can be prepared and has better C3H6Penetration rate and C3H6/C3H8The selective mixed matrix membrane, thereby better solving the technical problem of 'trade-off' effect.
In a second aspect, the application provides a preparation method of the MOF material with the surface grafted with the phospholipid bilayer, which adopts the following technical scheme:
a preparation method of an MOF material with a phosphine lipid bilayer grafted on the surface comprises the following steps:
firstly, uniformly dispersing a parent MOF material in a THF (tetrahydrofuran) solution of n-octadecyl phosphonic acid (OPA for short), controlling the temperature to be 25-35 ℃, stirring and reacting for 12-14h to bond metal in the parent MOF material and P in phosphonic acid groups in the OPA, and centrifugally drying the obtained reaction solution to obtain an OPA-parent MOF material which is marked as OPA-MOF;
then, uniformly dispersing the obtained OPA-MOF in an ethanol/THF mixed solution of cholesterol and lecithin, controlling the temperature to be 25-35 ℃, stirring and reacting for 12-14h to enable the cholesterol to be used as a bridge between octadecylphosphonic acid and lecithin, bridging a lecithin layer and octadecylphosphonic acid together, and centrifugally drying the obtained reaction solution to obtain an MOF material with a phosphine bilayer grafted on the surface, wherein the specific preparation steps are as follows:
(1) dispersing a parent MOF material into a THF solution of OPA with the concentration of 8-12mmol/L, stirring and mixing for 12-14h at room temperature to enable metal in the parent MOF material and P in the OPA to be bonded and connected, centrifuging the obtained reaction liquid at the controlled rotation speed of 8000-10000r/min, and drying the obtained precipitate at the controlled temperature of 25-30 ℃ to obtain OPA modified MOF material powder, which is marked as OPA-MOF;
the concentration of the THF solution of OPA is 8-12 mmol/L;
(2) dispersing the OPA-MOF obtained in the step (1) into an ethanol/THF mixed solvent containing cholesterol and lecithin, mixing and stirring at room temperature for 12-14h, then controlling the rotation speed to 8000-10000r/min for centrifugation, controlling the temperature of the obtained precipitate to 55-65 ℃ for drying, and obtaining OLC modified MOF powder, namely MOF material grafted with a phosphine bilayer on the surface, which is marked as OLC-MOF;
the ethanol/THF mixed solvent containing cholesterol and lecithin is formed by mixing a cholesterol ethanol solution and a lecithin THF solution, wherein the concentration of the cholesterol ethanol solution is 8-12mmol/L, the concentration of the lecithin THF solution is 8-12mmol/L, and in the ethanol/THF mixed solvent containing cholesterol and lecithin, the dosages of the cholesterol ethanol solution and the lecithin THF solution are as follows: the mass ratio of lecithin is 1:1 and mixing.
By adopting the technical scheme, because the metal (M) in the matrix MOF material has strong affinity to n-octadecyl phosphonic acid, a stable P-M bond is formed, so that the integrity of a framework of the MOF material with the phospholipid bilayer molecular layer grafted on the surface is kept, cholesterol is used as a bridge between n-octadecyl phosphonic acid and lecithin, and a lecithin layer and n-octadecyl phosphonic acid are bridged together, so that the preparation of the MOF material with the phospholipid bilayer grafted on the surface is successfully realized, and the preparation process is simple in process, easy to operate and considerable in scale production prospect.
Preferably, prior to the preparation of OPA-MOF, the parent MOF material is pre-treated, i.e. the parent MOF material is vacuum dried for 10-14h under a controlled vacuum of 0.01-0.02 Pa.
By adopting the technical scheme, the solvents in the parent MOF material during synthesis can be removed firstly, so that the influence of the existence of the solvents on the performance of the subsequent MOF material with the grafted phosphine bilayer on the surface is avoided.
Preferably, the concentration of the THF solution of the n-octadecyl phosphonic acid is 10 mmol/L; the concentration of the cholesterol ethanol solution in the ethanol/THF mixed solvent containing cholesterol and lecithin is 10mmol/L, the concentration of the lecithin THF solution is 10mmol/L, and the dosage of n-octadecyl phosphonic acid, cholesterol and lecithin is calculated according to the matrix MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of lecithin is 1: 5: 5: 5.
by adopting the technical scheme, the finally obtained MOF material with the surface grafted with the bilayer is used for preparing C through filling3H6/C3H8When the mixed matrix membrane is used for separation, it is used for C3H6/C3H8The screening effect of (a) will be better, whereas too high a concentration may block the channels of the parent MOF material, while too low a concentration may not fully effect the screening effect due to the incomplete OLC modification.
In a third aspect, the application provides an MOF material with a phospholipid bilayer grafted on the surface for preparing C3H6/C3H8Use of a mixed matrix membrane for separation.
By adopting the technical scheme, the MOF material with the surface grafted with the phospholipid bilayer is used as C3H6/C3H8Filler for use in preparation of mixed matrix membranes for separations to achieve C3H6/C3H8Separation of (4).
By adopting the technical scheme, the phosphate group in the lecithin in the phosphine bilayer of the MOF material with the surface grafted with the phosphine bilayer and the carbonyl in the high polymer formed after the polymerization of the polymer can be bonded and connected, and the cross-linking reaction between the lecithin in the phospholipid bilayer of the surface of the OLC-MOF material and the polymer forms a network structure. Thereby leading the pair C to be formed between the MOF material and the polymer with the surface grafted with the phosphine bilayer3H6/C3H8The gas channel with the screening effect is provided, meanwhile, the MOF material with the surface grafted with the phosphine bilayer has good compatibility with the polymer, so that the technical problem of poor compatibility between the filler and the polymer in the prior art is solved, and meanwhile, the C prepared by utilizing the MOF material with the surface grafted with the phosphine bilayer is utilized3H6/C3H8Mixed matrix membranes for separations with good C3H6Penetration rate and C3H6/C3H8Thereby also solving the technical problem of the "trade-off" effect.
In a fourth aspect, the present application provides C3H6/C3H8The preparation method of the mixed matrix membrane for separation adopts the following technical scheme:
c3H6/C3H8The preparation method of the mixed matrix membrane for separation comprises the steps of taking OLC-MOF material as filler, taking polymer, preferably polyethylene glycol diacrylate as matrix, and initiating the cross-linking polymerization reaction between the polyethylene glycol diacrylate and lecithin in the OLC-MOF material under the action of 2, 2-dimethoxy-2-phenylacetophenone (DMPA) serving as a photoinitiator under the irradiation of ultraviolet light to obtain C3H6/C3H8The preparation process of the mixed matrix membrane for separation specifically comprises the following steps:
(1) dispersing OLC-MOF materials into a methanol solution containing polyethylene glycol diacrylate (PEGDA), mixing and stirring for 3-5h, controlling the ultrasonic frequency to be 35-45Hz, performing ultrasonic treatment for 25-35min to uniformly disperse the materials to obtain a suspension, adding a photoinitiator 2, 2-dimethoxy-2-phenylacetophenone (DMPA) into the suspension, continuously stirring and uniformly mixing to obtain a uniformly dispersed prepolymer solution;
(2) placing the prepolymerization solution obtained in the step (1) between two quartz plates, wherein the distance between the two quartz plates is determined according to C to be prepared3H6/C3H8The thickness of the mixed matrix membrane for separation was determined (in the present application, only 1mm C)3H6/C3H8The separation of the mixed matrix membrane is illustrated without limiting the other thickness of C3H6/C3H8Preparation of mixed matrix membrane for separation), exposing to 312nm ultraviolet ray for 90s, and performing cross-linking polymerization reaction of polyethylene glycol diacrylate and lecithin in OLC-MOF to obtain C3H6/C3H8Crude product of mixed matrix membrane for separation;
(3) c obtained by the step (2) between two quartz plates3H6/C3H8Soaking the crude product of the mixed matrix membrane for separation in methanol solution for 3-5 days to remove unreacted polymer monomer polyethylene glycol diacrylate and initiator in the crude product of the mixed matrix membrane, and vacuum drying at 55-65 deg.C under the vacuum degree of 0.01Pa to obtain C3H6/C3H8The finished mixed matrix membrane for separation is designated as OLC-MOF/XLPOE membrane.
By adopting the technical scheme, the preparation process only adopts stirring, ultrasonic dispersion, methanol soaking and vacuum drying, so that the preparation process is simple, the operation is convenient, the large-scale production is convenient, and the C is finally obtained3H6/C3H8The mixed matrix membrane for separation has good C3H6Penetration rate and C3H6/C3H8Selectivity of (2).
Preferably, the OLC-MOF/XLPO film is prepared by using the raw materials OLC-MOF material, polyethylene glycol diacrylate and photoinitiator according to the proportion of OLC-MOF material: polyethylene glycol diacrylate: the mass ratio of the photoinitiator is 3: 7: 0.02.
by adopting the technical scheme, C is finally obtained3H6/C3H8The mixed matrix membrane for separation has better C3H6Penetration rate and C3H6/C3H8Selectivity of (2).
In a fifth aspect, the present application provides a C obtained by the above preparation method3H6/C3H8The mixed matrix membrane for separation adopts the following technical scheme:
c3H6/C3H8The mixed matrix membrane for separation is prepared from OLC-MOF material, polymer and photoinitiator, wherein the polymer is preferably polyethylene glycol diacrylate.
The OLC-MOF material, the polymer and the photoinitiator are preferably used in an amount such that the molar ratio of OLC-MOF material: polyethylene glycol diacrylate: the mass ratio of the photoinitiator is 3: 7: 0.02.
said C3H6/C3H8The mixed matrix membrane for separation is characterized in that P in phosphonic acid groups in n-octadecyl phosphonic acid in OLC on the surface of an OLC-MOF material is bonded and connected with metal in the MOF material, phosphate groups in lecithin in OLC are bonded and connected with carbonyl groups in a high polymer obtained after polymerization reaction of polymer polyethylene glycol diacrylate, and a molecular channel with the inner diameter of the channel being 0.40-0.42nm is formed between the OLC-MOF material and the polymer, so that the n-octadecyl phosphonic acid in OLC and the polymer are crosslinked into a net structure.
Advantageous technical effects of the present application
According to the MOF material with the surface grafted with the phospholipid bilayer, the P in the phosphonic acid group in the n-octadecyl phosphonic acid in the phospholipid bilayer grafted on the surface and the gold in the MOF materialBonding and connecting phosphate group in lecithin and carbonyl group in high polymer obtained by polymerization reaction of polymer polyethylene glycol diacrylate to form C-containing material between OLC-MOF material and polymer3H6/C3H8Molecular channels with sieving capacity with inner channel diameters of 0.40-0.42nm, and are thus useful for C3H6/C3H8Preparation of the separated mixed matrix membrane.
The MOF material with the surface grafted with the phosphine bilayer is used for preparing C3H6/C3H8Filler of mixed matrix membrane for separation, finally obtained C3H6/C3H8The mixed matrix membrane for separation has good C3H6Penetration rate and C3H6/C3H8Can be used for C3H6/C3H8Separation of (4). Finally obtained C3H6/C3H8The mixed matrix membrane for separation was tested at 30 ℃ under 0.3MPa, and C thereof3H6Has a permeation rate of 90-150Barrer, C3H6/C3H8The selectivity of (A) is 18 to 47.
Drawings
FIG. 1 and C3H6/C3H8A reaction mechanism diagram of the preparation process of the mixed matrix membrane for separation;
FIG. 2 is a sectional scanning electron micrograph of an OLC-ZIF-8/XLPOE film obtained in application example 1;
FIG. 3 is a sectional scanning electron microscope image of a ZIF-8/XLPOE film obtained in comparative example 1;
FIG. 4, scanning electron micrograph of cross section of pure XLPO film obtained in comparative example 2.
Detailed Description
The technical solution of the present application is further described below by means of several specific examples.
The model of the analytical equipment used in the embodiments of the present application and the information of the manufacturer are as follows:
gas chromatograph, model number (HP7890, Porapak N), produced by agilent corporation, usa;
Wicke-Kallenbach membrane basin, tianjin university of industry separation membrane and membrane process country focus laboratory;
the raw material information used in the examples of the present application is as follows:
polyethylene glycol diacrylate (PEGDA) with an average molecular weight of 700 and containing 100-300ppm BHT stabilizer (BHT is 2, 6-di-tert-butyl-4-methylphenol) purchased from Shanghai Michelin Biochemical technology Ltd;
2, 2-dimethoxy-2-phenylacetophenone (DMPA) with a purity of 99%, sigma aldrich trade ltd;
n-octadecyl phosphonic acid, 98% specification, Shanghai Bigdi pharmaceutical science and technology, Inc.;
lecithin, 98 in specification, available from Shanghai Bigdi pharmaceutical science and technology Co., Ltd;
cholesterol, 99% pure, sigma aldrich trade ltd;
absolute methanol, absolute ethanol and THF with the purity of 99 percent are purchased from national chemical reagent company Limited.
C of various mixed matrix membranes obtained in application examples of the present application3H6Penetration rate of C3H6/C3H8The selectivity determination method of (2) is as follows:
the prepared various mixed matrix membranes are placed in a Wicke-Kallenbach membrane pool (provided by national key laboratory of separation membrane and membrane process of Tianjin university of industry) supported by a porous sintered metal plate for gas performance test at 30 ℃ and under the pressure of 0.3 MPa. The effective area of the membrane was 0.785cm2The downstream side of the membrane is at atmospheric pressure. The Wicke-Kallenbach membrane pool is sealed by double O-shaped sealing rings, so that gas on the permeation side is prevented from leaking in the test process. By C3H6/C3H8The mixed gas of (2) is used as a feed gas, and helium is used as a purge gas. The gas at the permeation side is carried into a gas chromatograph by purge gas for analysis;
wherein C is3H6See the literature (D.H.Liu, L.Xiao, H.Chang, C.Q.Wang, Y.C.Pan, Y.S.Li, and Z.Y.Jiang.random matching between MOFs and polymers in mixed matrices for propylene/propane section.chemical Engineering Science 204(2019) 151-160.), and the apparatus used for the determination is a gas chromatograph of type (HP7890, Porapak N), available from Agilent, USA.
Wherein C is3H6/C3H8Selectivity (said C)3H6/C3H8The selectivity of the two-component mixed gas is a two-component mixed gas separation factor in the following formula
Figure BDA0003131210410000071
) See the literature (Koros W J, Ma YH, Shimidzu. T. terminolology for membranes and membrane processes (IUPAC Recommendations1996) [ J]Pure appl. chem., 1996, 68 (7): 1479-1489) the two-component mixed gas separation factor is defined as the volume ratio of the gas components on the permeate side (referred to as the side that has been separated) according to the IUPAC description of the membrane and membrane separation process (i.e., in the equation below)
Figure BDA0003131210410000072
) Volume ratio (i.e., in the following formula) to gas composition in the retentate side (which is the side to be separated)
Figure BDA0003131210410000073
) The ratio of (a) to (b), namely:
Figure BDA0003131210410000074
preparation example
Preparation example 1
The preparation method of the parent ZIF-8 material comprises the following steps:
at room temperature, 3g of zinc nitrate hexahydrate was added to 100mL of methanol, the resulting methanolic zinc nitrate solution was added directly to 100mL of methanol containing 6.6g of 2-methylimidazole, after standing for 24h, the resulting precipitate was washed 3 times with methanol by centrifugation at 9000rpm for 10min, and then vacuum dried to give the parent ZIF-8 material.
Preparation example 2
Preparation of parent ZIF-67 material, the steps were as follows:
at room temperature, 3g of cobalt nitrate hexahydrate was added to 100mL of methanol, the resulting cobalt nitrate methanol solution was directly added to 100mL of methanol solution containing 6.6g of 2-methylimidazole, after standing for 24h, the resulting precipitate was washed 3 times with methanol by centrifugation at 9000rpm for 10min, and then vacuum-dried to give the parent ZIF-67 material.
Preparation example 3
The preparation of the parent ZIF-71 material comprises the following steps:
0.7g of 4, 5-dichloroimidazole was dissolved in 64ml of N, N-Dimethylformamide (DMF) at room temperature, and the resulting 4, 5-dichloroimidazole N, N-dimethylformamide solution was directly added to 64ml of N, N-Dimethylformamide (DMF) containing 0.14g of zinc acetate dihydrate, reacted for 18h, and then centrifuged at 9000rpm for 10min, and the resulting precipitate was dried overnight under vacuum to give the parent ZIF-71 material.
Preparation example 4
The preparation method of the parent ZIF-90 material comprises the following steps:
at room temperature, 0.443g of zinc acetate hexahydrate is dissolved in 100ml of N, N-Dimethylformamide (DMF), the obtained zinc acetate hexahydrate N, N-dimethylformamide solution is completely added into 200ml of N, N-Dimethylformamide (DMF) solution in which 0.4g of aldehyde imidazole is dissolved, after mixing and stirring for 4 hours, the mixture is centrifuged at 9000rpm for 10min, and the precipitate is dried at 100 ℃ overnight, so that the parent ZIF-90 material is obtained.
Preparation example 5
Preparation of parent MOF-808 material, the steps were as follows:
h is to be3BTC (0.21g, 1mmol) and ZrOCl2·8H2O (0.97g, 3mmol) was dissolved in DMF/formic acid (45mL/45mL), placed under pressure in a Teflon-lined stainless steel vessel (100mL), heated to 130 ℃ for two days, the white precipitate was collected by filtration and washed 3 times with 20mL of fresh DMF, and the precipitate obtained after washing was washed successively with 100mL of fresh DMF, 100mL of deionized water,soaking in 100mL acetone for three days, and replacing fresh DMF, deionized water and acetone every day in the soaking process. After soaking, emptying at room temperature for 24h and at 150 ℃ for 24h in sequence to obtain a matrix MOF-808 material;
fresh DMF was used as described above, i.e. fresh DMF was taken.
Preparation example 6
The preparation of parent CuBTC material comprises the following steps:
h is to be3BTC (0.42g, 2mmol) and Cu (NO)3)2·3H2O (0.24g, 1mmol) was dissolved in ethanol/water (25mL/25mL), respectively, followed by Cu (NO)3)2·3H2Dropwise adding H into the O solution3Stirring the BTC solution at room temperature for 2h, centrifuging at 9000r/min for 10min to collect the blue precipitate, immersing in 50mL of ethanol for three days, changing the ethanol once a day, and vacuum drying the blue precipitate at 100 deg.C for 12h to obtain the parent CuBTC material.
Example 1
A MOF material with a surface grafted with a phosphine lipid bilayer specifically comprises the following steps:
(1) vacuum drying the parent ZIF-8 material obtained in preparation example 1 at 60 ℃ for 12h to obtain a pretreated parent MOF material, namely pretreated parent ZIF-8 powder;
(2) adding 0.3g of the pre-treated parent ZIF-8 powder obtained in the step (1) into 100mL of a THF solution of n-octadecyl phosphonic acid with the concentration of 10mmol/L, mixing and stirring for reaction for 12 hours to enable metal on the pre-treated parent MOF material to be bonded and connected with P in the n-octadecyl phosphonic acid, controlling the rotating speed of the obtained reaction liquid to be 9000r/min, centrifuging, controlling the temperature of the obtained precipitate to be 30 ℃, and drying to obtain n-octadecyl phosphonic acid modified ZIF-8 powder, which is marked as OPA-ZIF-8;
(3) dispersing the N-octadecyl phosphonic acid modified ZIF-8 powder in the step (2) into 100mL of mixed solution (the mixed solution is formed by mixing a cholesterol ethanol solution with the concentration of 10mmol/L and a lecithin THF solution with the concentration of 10mmol/L according to the volume ratio of 1: 1) at the temperature of 30 ℃), controlling the rotating speed to be 400r/min, stirring and reacting for 12h, taking cholesterol as a bridge between the N-octadecyl phosphonic acid and lecithin, bridging a lecithin layer and the N-octadecyl phosphonic acid together, controlling the rotating speed of the obtained reaction solution to be 9000r/min, centrifuging, controlling the temperature of the obtained precipitate obtained by centrifuging to be 60 ℃, and drying to obtain the modified ZIF-8 powder with a phosphine lipid bilayer (the phosphine lipid bilayer is simplified to be N-octadecyl phosphonic acid-cholesterol-lecithin, writing OLC), thus obtaining the ZIF-8 material with the surface grafted with the phosphine lipid bilayer and being marked as OLC-ZIF-8.
Examples 2 to 6
A MOF material with a surface grafted with a phosphine lipid bilayer specifically comprises the following steps:
only the parent ZIF-67 material, the parent ZIF-71 material, the parent ZIF-90 material, the parent MOF-808 material and the parent CuBTC material obtained in preparation examples 2-6 are respectively substituted for the parent ZIF-8 powder in the step (1) of example 1, and the rest are the same as example 1, and finally ZIF-67 powder, ZIF-71 powder, ZIF-90 powder, MOF-808 powder and CuBTC powder with OLC phospholipid bilayer modification are respectively obtained, namely the ZIF-67 material, the ZIF-71 material, the ZIF-90 material, the MOF-808 material and the CuBTC material with the surface grafted with the phospholipid bilayer are respectively marked as OLC-ZIF-67, OLC-ZIF-71, OLC-ZIF-90, OLC-MOF-808 and OLC-CuBTC.
Application example 1
C3H6/C3H8A mixed matrix membrane for separation, prepared by a method comprising the steps of:
(1) dispersing 0.3g of the ZIF-8 material (OLC-ZIF-8) with the surface grafted with the phosphine lipid bilayer obtained in the example 1 into a methanol solution of polyethylene glycol diacrylate (PEGDA) (the mass of PEGDA in the methanol solution of the polyethylene glycol diacrylate (PEGDA) is 0.7g, and the mass of methanol is 1g), stirring and mixing for 4 hours, then controlling the ultrasonic frequency to be 40Hz, performing ultrasonic dispersion for 30 minutes to obtain a suspension, then adding 0.002g of photoinitiator 2, 2-dimethoxy-2-phenylacetophenone (DMPA) into the suspension, and continuing stirring and reacting for 2 hours to obtain a uniformly dispersed prepolymer solution;
(2) placing the pre-polymerization solution between two quartz plates with a distance of 1mm, exposing the pre-polymerization solution for 90s under the ultraviolet ray of 312nm, and carrying out a polymerization reaction between the polyethylene glycol diacrylate and OLC-ZIF-8 to obtain C3H6/C3H8Crude product of mixed matrix membrane for separation;
(3) the compound C obtained in the step (2)3H6/C3H8Soaking the crude product of the mixed matrix membrane for separation in methanol solution for 3 days to remove unreacted monomer polyethylene glycol diacrylate and initiator in the mixed matrix membrane, and finally drying at 60 deg.C under the vacuum degree of 0.01Pa for 12h to obtain C3H6/C3H8The finished mixed matrix membrane for separation was designated OLC-ZIF-8/XLPOE membrane.
Comparative example 1 was used
C3H6/C3H8The preparation of the mixed matrix membrane for separation comprises the following specific steps:
the ZIF-8/XLPO membrane was obtained in the same manner as in application example 1, except that the ZIF-8 material having the phosphine lipid bilayer grafted on the surface thereof in step (1) of application example 1 was replaced with the ZIF-8 material obtained in preparation example 1.
Comparative example 2 was used
C3H6/C3H8The preparation of the mixed matrix membrane for separation comprises the following specific steps:
(1) dispersing 1g of polyethylene glycol diacrylate into 1g of methanol, mixing and stirring for 4h, performing ultrasonic treatment for 30min to uniformly mix the mixture, adding 0.002g of photoinitiator 2, 2-dimethoxy-2-phenylethylacetophenone (DMPA) into the mixed solution, and continuously stirring for 2h to obtain a uniform prepolymerization solution;
(2) placing the prepolymerization solution between two quartz plates with the distance of 1mm, and exposing the two quartz plates for 90s under the ultraviolet ray of 312nm to complete the polymerization process between the polyethylene glycol diacrylate to obtain a pure crude product of the XLPO membrane;
(3) and (3) soaking the pure XLPO membrane crude product obtained in the step (2) in methanol for 3 days to remove unreacted monomer polyethylene glycol diacrylate and an initiator in the pure XLPO membrane crude product, and finally, controlling the vacuum degree to be 0.01Pa and the temperature to be 60 ℃ to carry out drying for 12 hours to remove the solvent on the surface of the membrane, so as to obtain the pure XLPO membrane without the metal-organic framework material.
C of OLC-ZIF-8/XLPO membranes, ZIF-8/XLPO membranes and pure XLPO membranes obtained in application example 1, application control example 1 and application control example 23H6Penetration rate (Barrer) and C3H6/C3H8The results are shown in the following table:
Figure BDA0003131210410000111
as can be seen from the above table, the C of OLC-ZIF-8/XLPOE membrane prepared by grafting MOF material of phosphine bilayer on the surface of the present application3H6The permeation rate of the ZIF-8/XLPOE membrane is higher than that of the ZIF-8 membrane prepared by the ZIF-8 material3H6The permeation rate of the membrane is improved by 102.07 percent compared with the C of a pure XLPO membrane3H6The permeation rate of (c) was increased by 120.11%. Further, C of OLC-ZIF-8/XLPOE membrane prepared from MOF material with phosphine lipid bilayer grafted on surface3H6/C3H8Selectivity of (a) to (b) C of ZIF-8/XLPOE membrane prepared using ZIF-8 material3H6/C3H8The selectivity of the membrane is improved by 842.89 percent compared with the C of a pure XLPO membrane3H6/C3H8The selectivity of (a) is improved by 855.96%. Therefore, the mixed matrix membrane prepared from the MOF material with the surface grafted with the phosphine bilayer has good C3H6Penetration rate and C3H6/C3H8Can be used for C3H6/C3H8Separation of (4).
Further, cross-sectional scanning electron microscope results of the OLC-ZIF-8/XLPOE film, the ZIF-8/XLPOE film and the pure XLPOE film obtained in the application example 1, the application control example 1 and the application control example 2 are respectively shown in FIG. 2, FIG. 3 and FIG. 4, and it can be seen from the comparison of FIG. 2, FIG. 3 and FIG. 4 that the ZIF-8 with the surface grafted with the phosphine bilayer is dispersed in the polymer more uniformly in the OLC-ZIF-8/XLPOE film obtained in the application example 1, thereby showing that the ZIF-8 with the surface grafted with the phosphine bilayer has good compatibility with the polymer.
Application examples 2 to 6
In application example 1, OLC-ZIF-67, OLC-ZIF-71, OLC-ZIF-90, OLC-MOF-808 and OLC-CuBTC obtained in examples 2 to 6 were used in place of OLC-ZIF-8 in step (1), respectively, and OLC-ZIF-67/XLPOE, OLC-ZIF-71/XLPOE, OLC-ZIF-90/XLPOE, OLC-MOF-808/XLPOE and OLC-CuBTC/XLPOE were obtained in the same manner as in application example 1.
C of OLC-ZIF-67/XLPOE membranes, OLC-ZIF-71/XLPOE membranes, OLC-ZIF-90/XLPOE membranes, OLC-MOF-808/XLPOE membranes and OLC-CuBTC/XLPOE membranes obtained in application examples 2 to 6 described above3H6Penetration rate (Barrer) and C3H6/C3H8The selectivity of the mixture was measured by using the C values of the different mixed matrix membranes obtained in example 1 and examples 2 to 63H6Penetration rate (Barrer) and C3H6/C3H8The selectivity results are given in the following table:
Figure BDA0003131210410000112
Figure BDA0003131210410000121
the above table shows that, by using the MOF material grafted with the phosphine bilayer on the surface as the filler, the performance of the prepared mixed matrix membrane exceeds the upper limit of robeson, thereby better proving that a cross-linked screenable C can be formed between the MOF material grafted with the phosphine bilayer on the surface and the polymer3H6/C3H8Of the gas channel. C of the finally obtained mixed matrix film3H6Has a permeation rate of 80-150Barrer and C3H6/C3H8The selectivity of (A) is 18 to 47.
The gas channels in each of the mixed matrix membranes obtained in the above application examples 1 to 6 were measured, and the inner diameters of the gas channels were 0.40 to 0.42nm on average.
Example 7
A MOF material with a grafted phosphine lipid bilayer on the surface is prepared by the following steps:
(1) the same procedure as in step (1) of example 1;
(2) adding 0.46g of the pretreated parent MOF material in the step (1), namely the pretreated parent ZIF-8 powder, into 100mL of a THF solution of n-octadecyl phosphonic acid with the concentration of 8mmol/L, mixing and stirring for reaction for 12h, so that metal on the pretreated parent MOF material and P in the n-octadecyl phosphonic acid are bonded and connected, centrifuging the obtained reaction liquid by controlling the rotating speed to be 9000r/min, and drying the obtained precipitate at the temperature of 30 ℃ to obtain n-octadecyl phosphonic acid modified ZIF-8 powder, which is marked as OPA-ZIF-8;
(3) the method is the same as the step (3) in the example 1 except that the mixed solution is formed by mixing a cholesterol ethanol solution with the concentration of 8mmol/L and a lecithin THF solution with the concentration of 8mmol/L according to the volume ratio of 1:1, and the ZIF-8 material with the surface grafted with the phosphine bilayer is obtained and is marked as OLC-ZIF-8;
the amounts of n-octadecyl phosphonic acid, cholesterol and lecithin used for the above grafting were determined as the parent MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of lecithin is 1:4:4: 4.
Example 8
A MOF material with a grafted phosphine lipid bilayer on the surface is prepared by the following steps:
(1) the same procedure as in step (1) of example 1;
(2) adding 0.46g of the pretreated parent MOF material in the step (1), namely the pretreated parent ZIF-8 powder, into 100mL of 12mmol/L n-octadecyl phosphonic acid THF solution, mixing and stirring for reaction for 12h, so that metal on the pretreated parent MOF material and P in the n-octadecyl phosphonic acid are bonded and connected, centrifuging the obtained reaction liquid at a rotation speed of 9000r/min, and drying the obtained precipitate at a temperature of 30 ℃ to obtain n-octadecyl phosphonic acid modified ZIF-8 powder, which is marked as OPA-ZIF-8;
(3) the method is the same as the step (3) in the example 1 except that the mixed solution is formed by mixing a cholesterol ethanol solution with the concentration of 12mmol/L and a lecithin THF solution with the concentration of 12mmol/L according to the volume ratio of 1:1, and the ZIF-8 material with the surface grafted with the phosphine bilayer is obtained and is marked as OLC-ZIF-8;
the amounts of n-octadecyl phosphonic acid, cholesterol and lecithin used for the above grafting were determined as the parent MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of lecithin is 1:6:6: 6.
Application examples 7 to 8
In application example 1, the OLC-ZIF-8/XLPO membranes corresponding to example 7 and the OLC-ZIF-8/XLPO membranes corresponding to example 8 were obtained in the same manner as in application example 1 except that OLC-ZIF-8 obtained in examples 7 to 8 was used instead of OLC-ZIF-8 in step (1), respectively.
C of OLC-ZIF-8/XLPOE film obtained in application examples 7-83H6Penetration rate (Barrer) and C3H6/C3H8The selectivity of (A) was measured, and C of the mixed matrix membranes obtained in application examples 1 and 7 to 8 was finally used3H6Penetration rate (Barrer) and C3H6/C3H8The selectivity results are given in the following table:
Figure BDA0003131210410000131
as can be seen from the above table, in example 1, the concentration of the THF solution of n-octadecyl phosphonic acid is 10mmol/L, and the ethanol/THF mixed solvent containing cholesterol and lecithin is formed by mixing the ethanol solution of cholesterol and the THF solution of lecithin, wherein the ethanol solution of cholesterol is formed by mixing ethanol solution of cholesterol and the THF solution of lecithinThe concentration of the solution is 10mmol/L, the concentration of the lecithin THF solution is 10mmol/L, and the dosage of the n-octadecyl phosphonic acid, the cholesterol and the lecithin used for grafting is calculated according to the matrix MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of lecithin was 1: 5: 5:5, C of the obtained OLC-ZIF-8/XLPOE film3H6Penetration rate (Barrer) and C3H6/C3H8The selectivity of (A) is better. While the OLC-ZIF-8/XLPOE film obtained in application example 7 and application example 8 was used in C3H6Penetration rate (Barrer) and C3H6/C3H8The selectivity of the OLC-ZIF-8/XLPOE membrane was not as good as that of the OLC-ZIF-8/XLPOE membrane obtained in application example 1, and the reason for this was probably that the THF solution of n-octadecyl phosphonic acid, the ethanol/THF mixed solvent containing cholesterol and lecithin, at too high a concentration, may block the pores of the parent MOF material, and at too low a concentration, may not completely carry out good sieving effect for OLC modification.
In summary, the MOF material with the surface grafted with the phospholipid bilayer of the present application is used as a filler and a polymer to form a bridging-capable sieving C between the MOF material with the surface grafted with the phospholipid bilayer and the polymer in the process of preparing the mixed matrix membrane3H6/C3H8The inner diameters of other channels of the gas channel can reach 0.40-0.42nm, so that the obtained mixed matrix membrane has good C3H6Penetration rate and C3H6/C3H8Selectivity of (a), C of the finally obtained mixed matrix membrane3H6Has a permeation rate of 80-150Barrer and C3H6/C3H8The selectivity of (A) is 18 to 47.
The above-mentioned embodiments are merely illustrative and not restrictive, and those skilled in the art can modify the embodiments without inventive contribution as required after reading this description, but only fall within the scope of the claims of the present application.

Claims (8)

1. An MOF material with a grafted phosphine lipid bilayer on the surface is characterized in that the MOF material with the grafted phosphine lipid bilayer on the surface is formed by grafting a phosphine lipid bilayer consisting of n-octadecyl phosphonic acid-cholesterol-lecithin on a parent MOF material, a P-M bond is formed between a metal M on the parent MOF material and P in the n-octadecyl phosphonic acid in the phosphine lipid bilayer, the cholesterol in the phosphine lipid bilayer is used as a bridge between the n-octadecyl phosphonic acid and the lecithin, and the lecithin layer and the n-octadecyl phosphonic acid are bridged together;
the parent MOF material is ZIF-8, ZIF-67, ZIF-71, ZIF-90, MOF-808 or CuBTC;
the amounts of n-octadecyl phosphonic acid, cholesterol and lecithin used for the above grafting were determined as the parent MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of lecithin was 1:4-6: 4-6:4-6.
2. A MOF material having a surface grafted with a bilayer of phospholipids according to claim 1 wherein the amount of n-octadecyl phosphonic acid, cholesterol and lecithin used in the grafting is such that the ratio of the parent MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of lecithin was 1: 5: 5:5.
3. A method of preparing a MOF material having a surface grafted with a phospholipid bilayer according to claim 1 or 2, wherein:
firstly, uniformly dispersing a parent MOF material in a THF (tetrahydrofuran-tetrahydrofuran) solution of n-octadecyl phosphonic acid, controlling the temperature to be 25-35 ℃, stirring and reacting for 12-14h, and centrifugally drying the obtained reaction liquid to obtain the n-octadecyl phosphonic acid-parent MOF material which is marked as OPA-MOF;
then, uniformly dispersing the obtained OPA-MOF in an ethanol/THF mixed solution of cholesterol and lecithin, controlling the temperature to be 25-35 ℃, stirring and reacting for 12-14h, and centrifugally drying the obtained reaction solution to obtain an MOF material with a phosphine lipid bilayer grafted on the surface, wherein the MOF material is marked as an OLC-MOF material;
the concentration of the THF solution of the n-octadecyl phosphonic acid is 10 mmol/L;
the ethanol/THF mixed solvent containing cholesterol and lecithin is formed by mixing a cholesterol ethanol solution and a lecithin THF solution, wherein the concentration of the cholesterol ethanol solution is 10mmol/L, and the concentration of the lecithin THF solution is 10 mmol/L;
n-octadecylphosphonic acid, cholesterol and lecithin, as the parent MOF material: n-octadecyl phosphonic acid: cholesterol: the mass ratio of lecithin was 1: 5: 5:5.
4. MOF material surface-grafted with a phosphine bilayer according to claim 1 or 2 as preparation C3H6/C3H8Use of a filler for a mixed matrix membrane for separation.
5. C3H6/C3H8The preparation method of the mixed matrix membrane for separation is characterized by comprising the following steps:
(1) dispersing the MOF material with the surface grafted with the phosphine bilayer molecular layer according to the claim 1 or 2 into a polymer methanol solution with the mass percentage concentration of 65-75%, uniformly mixing and stirring, controlling the ultrasonic frequency to be 35-45Hz, and performing ultrasonic dispersion for 25-35min to obtain a suspension, then adding a photoinitiator 2, 2-dimethoxy-2-phenylacetophenone into the suspension, and continuously stirring and uniformly mixing to obtain a uniformly dispersed prepolymer solution;
the polymer is polyethylene glycol diacrylate;
(2) placing the prepolymerization solution between two quartz plates with the distance of 1mm, exposing for 85-95s under the ultraviolet ray of 312nm, and performing cross-linking polymerization reaction between the polyethylene glycol diacrylate and the MOF material with the surface grafted with the phosphine bilayer to obtain C3H6/C3H8Crude product of mixed matrix membrane for separation;
(3) c to be obtained3H6/C3H8Soaking the crude product of the mixed matrix membrane for separation in methanol solution for 3-5 days, and vacuum drying at 55-65 deg.C to obtain C3H6/C3H8And (3) preparing a mixed matrix membrane finished product for separation.
6. C obtained by the production process according to claim 53H6/C3H8A mixed matrix membrane for separation, prepared from raw materials consisting of OLC-MOF material, polymer and photoinitiator, the amounts of OLC-MOF material, polymer and photoinitiator being such that the molar ratio of OLC-MOF material: polymer (b): the mass ratio of the photoinitiator is 3: 7: 0.02.
7. the C of claim 63H6/C3H8The mixed matrix membrane for separation is characterized in that cross-linking reaction is carried out between lecithin in a phospholipid bilayer on the surface of an OLC-MOF material and a polymer to form a network structure, a P atom in a phosphonic acid group in n-octadecyl phosphonic acid in the phospholipid bilayer on the surface of the OLC-MOF material is bonded and connected with metal in the MOF material, and a phosphoric acid group in lecithin in the phospholipid bilayer is bonded and connected with a carbonyl group in a high polymer obtained after polymerization reaction of the polymer.
8. The C of claim 73H6/C3H8A mixed matrix membrane for separation, characterized in that C3H6/C3H8In the mixed matrix membrane for separation, molecular channels having an inner diameter of 0.40 to 0.42nm are formed between the OLC-MOF material and the high polymer.
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