CN106750440B - ZIF @ CNT modified polymer hybrid proton exchange membrane and preparation method thereof - Google Patents
ZIF @ CNT modified polymer hybrid proton exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of membranes, and particularly relates to a polymer hybrid proton exchange membrane modified by a carbon nanotube composite material coated by a zeolite imidazolate framework and a preparation method thereof. According to the invention, the ZIF (imidazole) framework (ZIF) fully-coated Carbon Nanotube (CNT) composite particles (ZIF @ CNT) are prepared firstly and uniformly dispersed in a polymer matrix, and the proton conductivity of the prepared ZIF @ CNT modified polymer hybrid proton exchange membrane is obviously improved compared with that of a pure polymer proton exchange membrane and is higher than that of the CNT modified polymer hybrid proton exchange membrane. Meanwhile, the strong interaction between imidazole and the polymer in the ZIF @ CNT further improves the fuel barrier capability of the hybrid proton exchange membrane. Therefore, the ZIF @ CNT modified polymer hybrid proton exchange membrane has more excellent selectivity. The method has the advantages of simple operation process, mild preparation conditions, low production cost, easy batch and large-scale production and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a polymer hybrid proton exchange membrane modified by a zeolite imidazolate framework and a carbon nanotube composite (ZIF @ CNT) and a preparation method thereof.
Background
Fuel Cells (FC) have excellent properties such as high energy conversion rate, no pollution, wide fuel sources, and low noise, and are now becoming one of the most competitive alternative power sources for internal combustion engines. Direct Methanol Fuel Cells (DMFCs), which are the sixth generation FCs, have the additional advantages of mild operating conditions, high energy density, long service life, and no need for fuel pretreatment devices, and have attracted extensive academic and industrial attention. A Proton Exchange Membrane (PEM) is one of the core components of a DMFC, and optimizing its performance plays a crucial role in developing a high performance DMFC. In one aspect, the PEM shields fuel (methanol, MeOH) from oxidant (often oxygen); PEM, on the other hand, provides a pathway for the migration of protons and/or hydrated protons. A high performance PEM should have both high proton conductivity and fuel barrier capability even under severe conditions of high temperature, low humidity and/or high fuel concentration.
The Metal Organic Frameworks (MOFs) have the characteristics of high specific surface area, high porosity and easily adjustable structure. Therefore, the catalyst has ideal application prospects in the aspects of catalysis, gas adsorption, separation, drug loading and the like. Recently, MOFs have gradually received a great deal of attention in proton conduction. Among them, ZIF-8, a common MOF, has been widely studied and applied to proton exchange membranes due to its good thermal and chemical stability and certain proton transfer capacity. Such as: material Chemistry A (Journal of materials Chemistry A2015 (3) 15838-15842) reported doping ZIF-8@ GO in Nafion to produce a ZIF-8@ GO modified proton exchange membrane with proton conductivity of 0.28S/cm at 120 deg.C, 40% RH, but not significantly improved at high humidity. ACS materials and surfaces (acsapplied materials and Interfaces 2016,8(35) 23015-23021) reports that the proton conductivity of the membrane at 140 ℃ under anhydrous conditions is 3.2 (± 0.12) × 10 "3S/cm, which is obviously improved compared with that of a pure polyethylene phosphate membrane, but as a proton exchange membrane mainly made of inorganic materials, the membrane has poor mechanical strength and short service life. The membrane science (Journal of membrane science 2016,499, 156-163) reported that ZIF-8 was incorporated into a PVA/PAMPS composite membrane matrix having a proton conductivity of 0.134S/cm at 80 ℃ with 100% humidity, which is a significant improvement over pure PVA/PAMPS, but with absolute values much lower than some of the commonly used commercial proton exchange membranes. Therefore, an ideal MOF structure is constructed for preparing a high-performance MOF modified hybrid proton exchange membrane, so that the hybrid membrane has excellent protonsConductivity remains the subject of considerable research.
According to the invention, a layer of zeolite imidazolate framework structure grows on the surface of a carbon nano tube in situ to prepare a carbon nano tube composite material (ZIF @ CNT) coated by a zeolite imidazolate framework, and the ZIF @ CNT-coated carbon nano tube composite material is doped in a polymer to obtain a boiling ZIF @ CNT-modified polymer hybrid proton exchange membrane. Due to the unique one-dimensional structure of the carbon nano tube, the ZIF grown on the surface shows excellent consistency, SO that imidazole in the ZIF and-SO in a polymer are mixed3H forms long-range continuous acid-base pair channels, and protons can be effectively transferred in the continuous acid-base pair channels, so that the proton conductivity of the hybrid membrane is greatly improved. And the prepared hybrid proton exchange membrane has excellent stability and low permeability to fuel. Namely, the high-performance polymer hybrid proton exchange membrane with the metal organic framework structure modified is prepared by the method.
Disclosure of Invention
The invention aims to provide a polymer hybrid proton exchange membrane modified by a zeolite imidazole ester framework-coated carbon nanotube composite (marked as ZIF @ CNT) with excellent performance and a preparation method thereof.
The invention provides a preparation method of a ZIF @ CNT modified polymer hybrid proton exchange membrane, which comprises the following specific steps:
(1) preparing 0.01-100 mg/L of carboxylated carbon nanotube CNT-COOH methanol dispersion liquid; then, adding metal salt and ligand imidazole compound with proper proportion, and mixing uniformly; placing the system in an environment with the temperature of 30-15 ℃ for 6-240 hours, then naturally cooling the system, and finally performing washing-centrifuging and other steps to obtain a carbon nano tube composite material coated by a zeolite imidazole ester framework, wherein the carbon nano tube composite material is marked as ZIF @ CNT;
(2) adding the required amount of ZIF @ CNT into the polymer solution, and uniformly dispersing to obtain a membrane casting solution; coating the casting solution into a film, placing the film in a drying oven at 40-8 ℃, and keeping for 6-24 hours; then, raising the temperature of the oven to 80-150 ℃, and keeping the temperature for 6-24 hours; and finally, carrying out acid soaking on the hybrid membrane to obtain the ZIF @ CNT modified polymer hybrid proton exchange membrane.
The metal salt is one or a mixture of zinc and cobalt metal salts, and the ligand imidazole compound is one or a mixture of imidazole and derivatives thereof.
In the invention, the addition amount of the metal salt and the ligand imidazole compound in the step (1) is 2-10 times of that of the carboxylated carbon nanotube.
In the invention, the ratio of the metal salt to the ligand imidazole compound in the step (1) is 1: 18-18: 1.
In the invention, the polymer solution in the step (2) is one or a mixture of several homogeneous solutions of perfluorinated sulfonic acid resin, sulfonated polyarylether, sulfonated polyaryl (thio) ether sulfone, sulfonated polyaryl (thio) ether ketone, sulfonated polyether sulfone ketone, sulfonated polyimide and derivatives thereof; the concentration of the polymer solution is 1-40 wt%, and the solvent of the polymer solution is a solvent for enabling the polymer to form a homogeneous solution.
In the invention, the step (2) is soaked in acid, and the acid is 1-4 mol/L hydrochloric acid, sulfuric acid or phosphoric acid or a mixture of several of the hydrochloric acid, the sulfuric acid or the phosphoric acid.
Compared with the previous work, the invention firstly prepares the 1D-shaped ZIF @ CNT and then dopes the ZIF @ CNT into the polymer to obtain a novel MOF modified composite proton exchange membrane. Wherein, the ZIF ligand is imidazole, namely, the composite particles contain a large amount of imidazole groups. On the one hand, the compatibility between the ZIF @ CNT and a polymer membrane matrix and the dispersibility of the ZIF @ CNT in a hybrid proton exchange membrane are improved; on the other hand, imidazole in the particles and sulfonate in the polymer interact to form more through and longer-range proton transfer channels, and the brand new channels effectively improve the proton conductivity of the composite membrane. Therefore, the proton conductivity of the ZIF @ CNT/polymer hybrid proton exchange membrane prepared by the method is far higher than that of a pure polymer proton exchange membrane. In addition, the introduction of the ZIF @ CNT composite nano particles greatly increases the tortuosity of a fuel permeation channel in the hybrid membrane, and the fuel permeability of the hybrid membrane is effectively inhibited.
The method has the advantages of simple operation process, mild preparation conditions, low production cost, easy batch and large-scale production, good industrial production basis and wide application prospect.
Drawings
FIG. 1 is a TEM image of ZIF @ CNT composite nanoparticles.
FIG. 2 is a temperature resolved proton conductivity of pure SPEEK membrane, ZIF @ CNT + SPEEK hybrid proton exchange membrane at 95% RH.
FIG. 3 is a graph of methanol permeability of pure SPEEK membranes, ZIF @ CNT + SPEEK hybrid proton exchange membranes at 30 ℃.
Detailed Description
The preparation of the ZIF @ CNT-modified polymer hybrid proton exchange membrane and the proton conduction performance thereof according to the present invention are further described in detail by the following examples. However, this example is provided only as an illustration and not as a limitation of the invention.
Example 1
1.120 mg CNT-COOH is ultrasonically dispersed in 30 mL methanol, then 0.2971 g zinc nitrate hexahydrate and 0.6568 g 2-methylimidazole are respectively weighed and respectively dissolved in 15 mL methanol, then the above CNT-CCOH dispersion liquid is poured into the above solution, the solution is transferred into a 100 mL polytetrafluoroethylene lining, a cover is covered and the reaction kettle is tightly sealed, then the reaction kettle is placed in a constant temperature oven at 90 ℃ for continuous reaction for 10 h, the reaction product is centrifugally separated, firstly fresh methanol solvent is continuously used for cleaning, the centrifugally separated product is finally placed in an oven at 50 ℃ for 6 h, and the ZIF @ CNT composite particles are obtained.
2. Taking 200 mg of SPEEK (sulfonation degree of 62%), adding 3mL of N, N-dimethylformamide, dissolving to form a SPEEK solution, adding 0.5 wt% of ZIF @ CNT into the polymer solution, and performing ultrasonic treatment for 3 hours to uniformly disperse the SPEEK solution; the dispersion was carefully poured into a mould and quickly placed in an oven at 60 ℃ for 8 h; then, the temperature was raised to 80 ℃ for 8 hours. Finally, the membrane was acidified with 1M HCl at room temperature for 48H to convert the membrane to H+And finally obtaining the ZIF @ CNT modified proton exchange membrane.
The proton conductivity of the proton exchange membrane prepared in the embodiment at 70 ℃ and 95% RH is as high as 0.28S/cm and is far higher than that of the proton exchange membrane prepared in the unmodified embodimentSPEEK proton exchange membranes (0.135S/cm). The methanol permeability at 30 ℃ is 3.92X 10-8cm2s-1Is reduced by 76.1 percent (16.43 multiplied by 10) compared with the unmodified Nafion proton exchange membrane-8cm2s-1). The proton conductivity was almost not decreased by a constant of about 3000min at 90 ℃ and 95% RH.
Example 2
1.120 mg CNT-COOH is ultrasonically dispersed in 30 mL methanol, then 0.2971 g zinc nitrate hexahydrate and 0.6568 g 2-methylimidazole are respectively weighed and respectively dissolved in 15 mL methanol, then the above CNT-CCOH dispersion liquid is poured into the above solution, the solution is transferred into a 100 mL polytetrafluoroethylene lining, a cover is covered and the reaction kettle is tightly sealed, then the reaction kettle is placed in a constant temperature oven at 90 ℃ for continuous reaction for 10 h, the reaction product is centrifugally separated, firstly fresh methanol solvent is continuously used for cleaning, the centrifugally separated product is finally placed in an oven at 50 ℃ for 6 h, and the ZIF @ CNT composite particles are obtained.
2. Taking 200 mg of SPEEK (sulfonation degree of 62%), adding 3mL of N, N-dimethylformamide, dissolving to form a SPEEK solution, adding 1 wt% of ZIF @ CNT into the polymer solution, and performing ultrasonic treatment for 3 hours to uniformly disperse the ZIEK solution; the dispersion was carefully poured into a mould and quickly placed in an oven at 60 ℃ for 8 h; then, the temperature was raised to 80 ℃ for 8 hours. Finally, the membrane was acidified with 1M HCl at room temperature for 48H to convert the membrane to H+And finally obtaining the ZIF @ CNT modified proton exchange membrane.
Example 3
1.120 mg CNT-COOH is ultrasonically dispersed in 30 mL methanol, then 0.2971 g zinc nitrate hexahydrate and 0.6568 g 2-methylimidazole are respectively weighed and respectively dissolved in 15 mL methanol, then the above CNT-CCOH dispersion liquid is poured into the above solution, the solution is transferred into a 100 mL polytetrafluoroethylene lining, a cover is covered and the reaction kettle is tightly sealed, then the reaction kettle is placed in a constant temperature oven at 90 ℃ for continuous reaction for 10 h, the reaction product is centrifugally separated, firstly fresh methanol solvent is continuously used for cleaning, the centrifugally separated product is finally placed in an oven at 50 ℃ for 6 h, and the ZIF @ CNT composite particles are obtained.
2. Get200 mg of SPEEK (sulfonation degree of 62%), adding 3mL of N, N-dimethylformamide, dissolving to form a SPEEK solution, adding 1.5wt% of ZIF @ CNT into the polymer solution, and performing ultrasonic treatment for 3h to uniformly disperse the ZIEK solution; the dispersion was carefully poured into a mould and quickly placed in an oven at 60 ℃ for 8 h; then, the temperature was raised to 80 ℃ for 8 hours. Finally, the membrane was acidified with 1M HCl at room temperature for 48H to convert the membrane to H+And finally obtaining the ZIF @ CNT modified proton exchange membrane.
Example 4
1.120 mg CNT-COOH is ultrasonically dispersed in 30 mL methanol, then 0.2971 g zinc nitrate hexahydrate and 0.6568 g 2-methylimidazole are respectively weighed and respectively dissolved in 15 mL methanol, then the above CNT-CCOH dispersion liquid is poured into the above solution, the solution is transferred into a 100 mL polytetrafluoroethylene lining, a cover is covered and the reaction kettle is tightly sealed, then the reaction kettle is placed in a constant temperature oven at 90 ℃ for continuous reaction for 10 h, the reaction product is centrifugally separated, firstly fresh methanol solvent is continuously used for cleaning, the centrifugally separated product is finally placed in an oven at 50 ℃ for 6 h, and the ZIF @ CNT composite particles are obtained.
2. Taking 200 mg of SPEEK (sulfonation degree of 62%), adding 3mL of N, N-dimethylformamide, dissolving to form a SPEEK solution, adding 2 wt% of ZIF @ CNT into the polymer solution, and performing ultrasonic treatment for 3 hours to uniformly disperse the ZIEK solution; the dispersion was carefully poured into a mould and quickly placed in an oven at 60 ℃ for 8 h; then, the temperature was raised to 80 ℃ for 8 hours. Finally, the membrane was acidified with 1M HCl at room temperature for 48H to convert the membrane to H+And finally obtaining the ZIF @ CNT modified proton exchange membrane.
Example 5
1.120 mg CNT-COOH is ultrasonically dispersed in 30 mL methanol, then 0.2971 g zinc nitrate hexahydrate and 0.6568 g 2-methylimidazole are respectively weighed and respectively dissolved in 15 mL methanol, then the above CNT-CCOH dispersion liquid is poured into the above solution, the solution is transferred into a 100 mL polytetrafluoroethylene lining, a cover is covered and the reaction kettle is tightly sealed, then the reaction kettle is placed in a constant temperature oven at 90 ℃ for continuous reaction for 10 h, the reaction product is centrifugally separated, firstly fresh methanol solvent is continuously used for cleaning, the centrifugally separated product is finally placed in an oven at 50 ℃ for 6 h, and the ZIF @ CNT composite particles are obtained.
2. Taking 200 mg of SPEEK (sulfonation degree of 62%), adding 3mL of N, N-dimethylformamide, dissolving to form a SPEEK solution, adding 2.5 wt% of ZIF @ CNT into the polymer solution, and performing ultrasonic treatment for 3 hours to uniformly disperse the ZIEK solution; the dispersion was carefully poured into a mould and quickly placed in an oven at 60 ℃ for 8 h; then, the temperature was raised to 80 ℃ for 8 hours. Finally, the membrane was acidified with 1M HCl at room temperature for 48H to convert the membrane to H+And finally obtaining the ZIF @ CNT modified proton exchange membrane.
Claims (6)
1. A preparation method of a polymer hybrid proton exchange membrane based on imidazolyl metal organic framework modification is characterized by comprising the following specific steps:
(1) preparing 0.01-100 mg/L of carboxylated carbon nanotube CNT-COOH methanol dispersion liquid; then, adding metal salt and ligand imidazole compound with proper proportion, and mixing uniformly; placing the system in an environment with the temperature of 30-15 ℃ for 6-240 hours, then naturally cooling the system, and finally performing a washing-centrifuging step to obtain a carbon nano tube composite material coated by a zeolite imidazole ester framework, wherein the composite material is marked as ZIF @ CNT;
(2) adding the required amount of ZIF @ CNT into the polymer solution, and uniformly dispersing to obtain a membrane casting solution; coating the casting solution into a film, placing the film in a drying oven at 40-8 ℃, and keeping for 6-24 hours; then, raising the temperature of the oven to 80-150 ℃, and keeping the temperature for 6-24 hours; finally, carrying out acid soaking on the hybrid membrane to obtain a ZIF @ CNT modified polymer hybrid proton exchange membrane;
the metal salt is one or a mixture of zinc and cobalt metal salts, and the ligand imidazole compound is one or a mixture of imidazole and derivatives thereof.
2. The preparation method according to claim 1, wherein the addition amount of the metal salt and the ligand imidazole compound in the step (1) is 2-10 times of that of the carboxylated carbon nanotube.
3. The preparation method according to claim 1, wherein the ratio of the metal salt to the ligand imidazole compound in step (1) is 1: 18-18: 1.
4. The method according to claim 1, 2 or 3, wherein the polymer solution in step (2) is one of homogeneous solutions of perfluorosulfonic acid resin, sulfonated polyarylether, sulfonated polyarylethersulfone, sulfonated polyarylethersulfoether sulfone, sulfonated polyaryletherketone, sulfonated polyarylethersulfoether ketone, sulfonated polyethersulfone ketone, sulfonated polyimide and its derivatives, or a mixture of several of them; the concentration of the polymer solution is 1-40 wt%, and the solvent of the polymer solution is a solvent for enabling the polymer to form a homogeneous solution.
5. The preparation method according to claim 1, 2 or 3, characterized in that the acid soaked in step (2) is 1-4 mol/L hydrochloric acid, sulfuric acid or phosphoric acid, or a mixture of several of them.
6. A ZIF @ CNT-modified polymeric hybrid proton exchange membrane prepared by the preparation process of any one of claims 1-5.
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| CN106750440A (en) | 2017-05-31 |
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