CN113527705A - Metal organic framework material and preparation method thereof, proton exchange membrane and preparation method thereof, and fuel cell - Google Patents

Metal organic framework material and preparation method thereof, proton exchange membrane and preparation method thereof, and fuel cell Download PDF

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CN113527705A
CN113527705A CN202110844699.XA CN202110844699A CN113527705A CN 113527705 A CN113527705 A CN 113527705A CN 202110844699 A CN202110844699 A CN 202110844699A CN 113527705 A CN113527705 A CN 113527705A
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exchange membrane
proton exchange
organic framework
framework material
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马海庆
肖森林
贺迪华
马杰
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Shenzhen Hydrogen Age New Energy Technology Co ltd
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
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Abstract

The invention discloses a metal organic framework material and a preparation method thereof, a proton exchange membrane and a preparation method thereof, and a fuel cell, wherein the molecular formula of the metal organic framework material is (NH)4)4[TcMo2(OX)6(Atz)2]3Wherein OX is oxalic acid, Atz is 3-amino-1, 2, 4-triazole, and the proton exchange membrane comprises a polymer substrate and the metal organic framework material dispersed in the polymer substrate. The proton exchange membrane prepared by the invention can be used at high temperature and without water stripsHigh proton conductivity, low methanol permeability, and good chemical and thermal stability are achieved under conditions.

Description

Metal organic framework material and preparation method thereof, proton exchange membrane and preparation method thereof, and fuel cell
Technical Field
The invention relates to the technical field of fuel cells, in particular to a metal organic framework material and a preparation method thereof, a proton exchange membrane and a preparation method thereof, and a fuel cell.
Background
The new high temperature proton exchange membranes with high proton conductivity at temperatures above 100 ℃ can eliminate some of the serious problems facing fuel cells.
Introduction of heterocyclic compounds (e.g., imidazole, etc.) into polymer-formed high-temperature proton exchange membranes has been a hot spot of recent research because heterocyclic compounds can conduct protons in a high-temperature environment of 100 ℃ or higher. However, the heterocyclic compound has a small molecular structure and is easily leached, so that the proton conductivity of the fuel cell is continuously reduced during operation.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a metal organic framework material and a preparation method thereof, a proton exchange membrane and a preparation method thereof and a fuel cell.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a metal organic framework material is characterized in that the molecular formula is (NH)4)4[TcMo2(OX)6(Atz)2]3Wherein OX is oxalic acid, and Atz is 3-amino-1, 2, 4-triazole.
The invention also discloses a preparation method of the metal organic framework material, which comprises the following steps:
dissolving oxalic acid, 3-amino-1, 2, 4-triazole, ammonium permanganate, soluble technetium salt and soluble molybdenum salt in a solvent to obtain a reaction solution;
and placing the reaction solution in a closed space for solvothermal reaction to obtain the metal organic framework material.
The invention also discloses a proton exchange membrane which comprises a polymer substrate and the metal organic framework material dispersed in the polymer substrate, wherein the metal organic framework material is divided intoHas the sub-formula of (NH)4)4[TcMo2(OX)6(Atz)2]3Wherein OX is oxalic acid, and Atz is 3-amino-1, 2, 4-triazole.
The invention also discloses a preparation method of the proton exchange membrane, which comprises the following steps:
providing a slurry of a polymeric substrate;
providing a metal organic framework material having a molecular formula of (NH)4)4[TcMo2(OX)6(Atz)2]3Wherein OX is oxalic acid, and Atz is 3-amino-1, 2, 4-triazole;
dispersing the metal organic framework material in the slurry of the polymer substrate to obtain the slurry of the proton exchange membrane, and curing the slurry of the proton exchange membrane to obtain the proton exchange membrane.
The invention also discloses a fuel cell comprising the proton exchange membrane.
The embodiment of the invention has the following beneficial effects:
the molecular formula of the synthetic method is (NH)4)4[TcMo2(OX)6(Atz)2]3The metal organic framework material encapsulates the heterocyclic compound Atz with proton conductivity at a specific position of the metal organic framework material to form a stable proton transmission channel, thereby not only avoiding the leaching of the heterocyclic compound Atz, but also improving the proton conductivity of the fuel cell.
The embodiment of the invention enables the formation of a metal organic framework material with high crystallinity by adding oxalic acid as a common organic ligand of Atz.
Experiments prove that the proton exchange membrane prepared by the invention can realize high proton conductivity, low methanol permeability and good chemical and thermal stability under the conditions of high temperature and no water.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Wherein:
FIG. 1 is a schematic representation of the three-dimensional atomic structure of the metal-organic framework material of the present invention.
FIG. 2a is a graph comparing the XRD pattern of a metal organic framework material made in accordance with an embodiment of the present invention with the XRD pattern of the metal organic framework material modeled and established as shown in FIG. 1.
FIG. 2b is a SEM picture of the metal organic framework material of FIG. 2a according to an embodiment of the present invention.
FIG. 3 is a FT-IR spectrum of the metal-organic framework material shown in FIG. 2 b.
Figure 4 is a TGA plot of the metal-organic framework material shown in figure 2b at a temperature ramp rate of 10 degrees/minute.
FIG. 5a is a SEM image of a linear metal organic framework material prepared under an electric field of 50kV/m according to an embodiment of the present invention.
FIG. 5b is a SEM image of a linear metal organic framework material prepared under an electric field of 10kV/m according to an embodiment of the present invention.
FIG. 5c is a photograph of a proton exchange membrane made from SPES doped with the metal organic framework material in the form of a wire of FIG. 5 a.
Figure 5d is a photograph of the nanowire proton exchange membrane formed after hot pressing the proton exchange membrane shown in figure 5 c.
Figure 5e is a HRTEM picture of the proton exchange membrane shown in figure 5c after staining with lead acetate.
Figure 5f is an SEM picture of the nanowire proton exchange membrane shown in figure 5 d.
FIG. 6 shows PES and PES-SO2H and PES-SO2IR spectrum of Cl.
Figure 7 is an IR spectrum of the nanowire proton exchange membrane shown in figure 5 d.
Fig. 8 is an X-ray diffraction pattern of the metal organic framework material and the nanowire proton exchange membrane prepared in one embodiment of the present invention, and an X-ray diffraction pattern of the nanowire proton exchange membrane after a conductivity test at 160 ℃.
FIG. 9 is a diagram of MOFs-PES-SO aligned by applying an electric field2Cl composite proton exchange membrane, MOFs-PES-SO in non-directional arrangement without electric field application2The relationship between the temperature and the proton conductivity of the Cl composite proton exchange membrane and the Nifion-115 membrane is shown.
FIG. 10 a shows MOFs-PES-SO aligned by applying electric field2The nanowire in the Cl composite proton exchange membrane and the structure schematic diagram of the distribution of MOFs in the nanowire, b is the MOFs-PES-SO which directionally arranges the applied electric field2HRTEM image of Cl composite proton exchange membrane after being placed in saturated lead acetate solution for dyeing.
FIG. 11 is a schematic diagram of two proton conducting paths in Atz.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Metal organic framework Materials (MOFs) are a new class of porous crystalline materials with high specific surface area, controllable structure and potential electrochemical properties, whose internal pores can store proton charge carriers (water, acids, heterocyclic compounds) to immobilize them. The present invention aims to design and synthesize MOFs having good proton conductivity to overcome the problems of easy leaching of heterocyclic compounds and poor proton conductivity.
The inventors originally tried to synthesize MOFs using heterocyclic compounds in combination with different metals, however, no highly crystalline structure was produced. The inventors tried to add oxalic acid as a co-ligand to the heterocyclic compound Atz, resulting in a highly crystalline structure showing significant proton conductivity under high temperature and anhydrous conditions.
The invention discloses metal organic framework materials MOFs, the molecular formula of which is (NH)4)4[TcMo2(OX)6(Atz)2]3·4H2O, wherein OX is oxalic acid, Atz is 3-amino-1, 2, 4-triazole, and a highly crystalline structure is obtained by adding oxalic acid as a co-ligand of the heterocyclic compound Atz.
The preparation method of the metal organic framework material comprises the following steps:
step S1: dissolving oxalic acid, 3-amino-1, 2, 4-triazole (Atz), ammonium permanganate, soluble technetium salt and soluble molybdenum salt in a solvent to obtain a reaction solution. Wherein the molar ratio of molybdenum element in the soluble molybdenum salt to technetium element in the soluble technetium salt is 1: 1-1: 2, and the molar ratio of technetium element in the soluble technetium salt to Atz is 1: 2.
In one embodiment, the soluble technetium salt is technetium (IV) chloride and the soluble molybdenum salt is molybdenum (III) chloride.
Step S2: and placing the reaction solution in a closed space for solvothermal reaction to obtain the metal organic framework material.
In this step, the temperature of the solvothermal reaction is specifically 150 ℃ to 200 ℃.
The invention also discloses a proton exchange membrane which comprises a polymer substrate and a metal organic framework material dispersed in the polymer substrate, wherein the chemical formula of the metal organic framework material is (NH)4)4[TcMo2(OX)6(Atz)2]3·4H2O, wherein OX is oxalic acid, Atz is 3-amino-1, 2, 4-triazole, and the chemical structural formula of Atz is shown in the specification
Figure BDA0003180055680000051
The mobility of the mass is reduced due to the bulk and grain boundaries of the MOFs, resulting in shorter distance conductivity and discontinuous proton conductivity. To solve this problem, in one embodiment, the metal organic framework material is oriented, which can shorten the distance between adjacent MOFs and improve proton conductivity.
Further, in order to improve compatibility between the MOFs and the polymer substrate, it is preferable that the polymer substrate includes an aromatic ring structure or an aromatic heterocyclic structure, and the aromatic ring structure or the aromatic heterocyclic structure is aligned with the metal-organic framework material. The aromatic ring structure or the aromatic heterocyclic structure has a conjugated planar ring system, and a proton transmission channel is formed after the oriented arrangement. The aromatic ring structure may be a benzene ring, the aromatic heterocyclic structure may be one in which one or more C atoms in the benzene ring are substituted with a heteroatom, which may be N, O, S or the like.
Further, the polymer substrate may also include chlorosulfonic acid groups, i.e., -SO2Cl groups, on the one hand chlorosulfonic acid groups, which can conduct protons, and on the other hand chlorosulfonic acid groups, which can react with-NH in Atz in MOFs2The groups react to form sulfonamide groups, and thus, the compatibility between the polymer substrate and the MOFs may be improved.
Further, the polymer substrate is polyether sulfone containing chlorosulfonic acid group, and is marked as PES-SO2And (4) Cl. The polyether sulfone contains a benzene ring structure, the benzene rings in the polyether sulfone can be directionally arranged together with MOFs, and PES-SO2-SO in Cl2Cl and-NH in Atz2Form stronger sulfonamide bond, SO that PES-SO2The combination of Cl and MOFs can form a nanowire structure, the nanowire provides a long-range and continuous channel for proton transmission, and results show that the membrane can remarkably improve proton conductivity, and in addition, the nanowire structure is stable, high temperature resistance is realized, and methanol permeability is improved.
In one embodiment, the mass of the metal organic framework material accounts for 10% to 50% of the total mass of the proton exchange membrane.
The invention also discloses a preparation method of the proton exchange membrane, which comprises the following steps:
step S1: a polymeric substrate is provided.
In one embodiment, the polymer substrate is PES-SO2Cl。
PES-SO2The preparation method of Cl comprises the following steps:
step S11: adding polyether sulfone (PES) into concentrated sulfuric acid (98%) to make reaction so as to obtain first product. In this process, Polyethersulfone (PES) was added to concentrated sulfuric acid (98%) and stirred continuously to form a homogeneous solution.
Step S12: gradually and slowly adding chlorosulfonic acid into the first product obtained in the step S11, continuously stirring at the temperature of below 10 ℃, and obtaining a second product after the reaction is finished.
Step S13: and pouring the second product into ice water, filtering and recovering the precipitate to obtain the sulfonated polyether sulfone.
Step S2: preparing MOFs, dissolving oxalic acid, Atz, high ammonium manganite, soluble technetium salt and soluble molybdenum salt in a solvent to obtain a reaction solution, and placing the reaction solution in a closed space to perform solvothermal reaction at the temperature of 150-200 ℃ to obtain the MOFs.
The molar ratio of molybdenum to technetium is 1: 1-1: 2, and the molar ratio of technetium to Atz is 1: 2.
Step S3: and (3) placing the MOFs into a solution of a polymer substrate, and solidifying the polymer substrate to obtain the proton exchange membrane.
In this step, after the MOFs is placed in the solution of the polymer substrate, an electric field is applied, and then the polymer substrate is cured, under the action of the electric field, the MOFs and the polymer substrate are aligned.
In one embodiment, the electric field strength is 20 kV/m-80 kV/m, so that the MOFs and the polymer substrate can be directionally arranged to form a nanowire-like structure.
After curing the polymer substrate, the method further comprises step S4: the hot-pressed proton exchange membrane, the MOFs and the polymer substrate can be directionally arranged to form a nanowire structure, and then the nanowire structure can be more stable through hot pressing.
The invention also discloses a fuel cell comprising the proton exchange membrane.
The following are specific examples.
Example 1
And preparing the MOFs.
According to the stoichiometric ratio of MOFs molecular formula, 0.1g of oxalic acid, 0.4g of Atz, 0.1g of high ammonium manganite, 0.2g of technetium chloride and 0.1g of molybdenum chloride are dissolved in 0.5mL of water to obtain a reaction solution, and the reaction solution is placed in a closed space to carry out solvothermal reaction at 180 ℃ to obtain the MOFs.
Example 2
And preparing the proton exchange membrane.
1) Preparation of PES-SO2And (4) Cl samples. 20 g of Polyethersulfone (PES) were added to 20ml of concentrated sulfuric acid (98%) in a three-necked reaction flask and heated to 90 ℃ and stirred at room temperature for about 2 hours to form a homogeneous solution. Adding 10ml of chlorosulfonic acid (ClSO)2OH, 0.15mol) was dissolved in 30ml of 98% concentrated H2SO4Uniformly mixing, gradually and slowly dripping the mixture into a polyether sulfone solution by sucking the mixture by a dropper, stirring the solution at the speed of 800rpm at the temperature of 10 ℃ for 3 hours, pouring the obtained product into acetone after the reaction is finished to form white precipitate, filtering to obtain a filter material, dissolving the filter material into DMAc, re-precipitating the filter material in ether, washing the filter material to be neutral by acetone after the filtration, and drying the filter material in vacuum at the temperature of 120 ℃ for 24 hours to obtain pure PES-SO2Cl membrane, PES-SO2Dissolving Cl membrane in DMF and chloride, and filtering to obtain final PES-SO2And (5) washing the Cl membrane with water for later use.
2) A proton exchange membrane 1 is prepared. Taking 0.75g of PES-SO prepared in the step 1)2The Cl film was dissolved in a solution of NMP and NaOH having a concentration of 0.1mol/L, 0.25g of MOFs obtained in example 1 was added, treated in an ultrasonic bath for 40 minutes, and then stirred for 3 days to obtain a uniform film solution. And pouring the membrane solution on an aluminum casting plate, inserting a positive electrode and a negative electrode into the membrane solution, wherein the distance between the positive electrode and the negative electrode is 20cm, and performing electric polling for 24h-48 h under an electric field of 50kV/m to obtain the proton exchange membrane 1 in directional arrangement.
3) A proton exchange membrane 2 is prepared. Hot pressing the proton exchange membrane 1 to obtain the proton exchange membrane 2.
Comparative example 1
A commercial Nafion-115 membrane was used as comparative example 1.
Comparative example 2
The proton exchange membrane 3 is prepared, and the proton exchange membrane 3 is different from the proton exchange membrane 1 only in that the electric field intensity is 10kV/m, and the rest is the same.
Comparative example 3
The proton exchange membrane 4 is prepared, and the proton exchange membrane 4 is different from the proton exchange membrane 1 only in that an electric field is not applied, and the rest is the same.
Test example 1
Referring to fig. 1, a dotted frame in fig. 1 marks a five-membered heterocyclic structure, and atom numbers of atoms are marked at lattice boundaries, N denotes a nitrogen atom, O denotes an oxygen atom, M denotes a metal Mo or Tc, C denotes a carbon atom, H denotes a hydrogen atom, other atoms not marked with atoms are marked with atoms, the smallest sphere is a hydrogen atom, the largest sphere is a metal atom, C, O is similar to the size of the N atom, the MOFs is similar to β -quartz in structure, and the MOFs is a large purple parallelepiped prepared by a solvothermal reaction of oxalate, ammonium permanganate, technetium (IV) chloride and molybdenum (III) chloride in water. Each molybdenum ion is combined with three oxalate ligands to form a distorted D3 unit and a six-coordinate distorted oxygen octahedron, the Mo-O bond distance is between 1.963 and 1.987 angstroms, each Mo atom is positioned at a universal position, three oxalate and permanganate units form a helical structure, one oxalate ligand points to a crystallization water molecule along the helical axis, the other two oxalate ligands bridge molybdenum and technetium ions in a bidentate mode, and conversely, each technetium (II) ion is positioned at three C2The axes cross and are connected to four molybdenum (III) s by oxalate bridges, so that the coordination number of the technetium atom is 8 and the compound exhibits a stoichiometric ratio of Mo to Tc of 2: 1.
Referring to FIGS. 2a and 2b, which are graphs comparing the XRD patterns of MOFs prepared in example 1 of the present invention with the XRD patterns of the MOFs established by simulation shown in FIG. 1, it can be seen that: XRD diffraction peaks of MOFs prepared in example 1 correspond to diffraction peaks of MOFs established in a simulation mode one by one.
Referring to FIG. 3, FI-IR spectra show the presence of Atz contained in the MOFs structure, again confirming the structure of the MOFs.
Referring to the TGA curve of the MOFs of fig. 4, two weight loss steps can be observed during heating from 30 ℃ to 600 ℃: the first step occurs at 50 ℃ to 100 ℃ due to solvent evaporation losses; the second loss step, starting from 300 ℃, is the result of the decomposition of the MOFs. Clearly, MOFs are thermally stable at temperatures ranging from 100 ℃ to 300 ℃ and can stabilize chelating rigid linkers.
Referring to fig. 5a to 5f, it can be seen that: the electric field intensity is too small, and the obtained MOFs cannot be sufficiently aligned, so that the electric field intensity of the MOFs aligned in the present invention is preferably 20kV/m to 80 kV/m.
Referring to FIG. 6, PES-SO are shown2H and PES-SO2IR spectrum of Cl 1374cm in the IR spectrum-1The asymmetric stretching peak at the position proves that the-SO2Successful formation of Cl. Referring to FIG. 7, MOFs-PES-SO2-SO in Cl composite nanowire proton exchange membrane (namely proton exchange membrane 2)2Cl at 1374cm-1The peak at (B) completely disappeared and appeared to be 1310cm-1New peak at (b), corresponding to-SO2NH2And the groups prove that when the MOFs is fused with the SPES, ammonium groups in the MOFs react with chlorosulfonic acid to form a new chemical bond, namely, a sulfonic acid amine bond, so that phase separation between two phases of the MOFs and the SPES is avoided, and the proton conductivity of the final proton exchange membrane is improved.
Test example 2
X-ray diffraction test
The samples were XRD characterized by a japanese Dmax X-ray diffractometer equipped with graphite monochromating high intensity Cu-Ka radiation.
Referring to fig. 8, it can be seen that: all strong diffraction peaks of the proton exchange membrane 2 correspond to strong diffraction peaks in the MOFs structure, and after the conductivity test is carried out at 160 ℃, the strong diffraction peaks of the MOFs still exist, which indicates that the MOFs still keeps stable in structure in the high-temperature and high-pressure working environment of the fuel cell.
The mechanical properties of the proton exchange membrane 2, including Tensile Strength (TS) and elongation at break (Eb), were measured at different temperatures. All membranes exhibit good mechanical properties, even at high temperatures, sufficient to act as proton exchange membranes. The mechanical strength of the nanowires can be significantly improved because the polymer within the uniaxially aligned nanowires is strongly oriented in the axial direction of the nanowires.
Test example 3
And (5) testing oxidation stability.
The invention also carries out oxidation stability test on the proton exchange membrane, and the proton exchange membrane is not subjected to oxidation stability testThe proton exchange membrane 4 prepared by applying an electric field, the proton exchange membrane 3 prepared by applying an electric field of 10kV/m and not sufficiently aligned with the MOFs, and the proton exchange membrane 2 prepared by applying an electric field of 50kV/m and sufficiently aligned with the MOFs are respectively soaked in a Fenton reagent (the Fenton reagent comprises 2ppm of FeSO4And 3 wt.% of hydrogen peroxide), recording the time for starting dissolving the membrane, wherein the proton exchange membrane 4 prepared without applying an electric field starts dissolving after 5.4 hours, the oxidation stability is the worst, the proton exchange membrane 3 prepared by applying the electric field and not fully aligned with the MOFs starts dissolving after 8.9 hours, and the proton exchange membrane 2 prepared by applying the electric field and fully aligned with the MOFs starts dissolving after 10.2 hours, so that the MOFs-SPES composite proton exchange membrane prepared by fully aligned with the MOFs has the highest oxidation stability.
Test example 4
Proton conductivity test
Referring to fig. 9, it can be seen from fig. 9 that: the proton exchange membrane 2 and the proton exchange membrane 4 both contain MOFs, so that compared with a Nafine-115 membrane, the proton conductivity is obviously improved, the oriented proton exchange membrane 2 prepared by applying an electric field also has higher proton conductivity than the non-oriented proton exchange membrane 4, and the proton conductivity is improved more obviously along with the increase of the temperature. It can also be seen from fig. 9: the proton conductivity of the proton exchange membrane 2 and the proton exchange membrane 4 containing the MOFs is not reduced at the temperature of more than 100 ℃, while the proton conductivity of the Nafine-115 membrane is remarkably reduced along with the increase of the temperature, which shows that the addition of the MOFs enables the proton exchange membrane to conduct the proton under the high-temperature and anhydrous environment, which is attributed to the proton conductivity of heterocyclic compounds in the MOFs.
Test example 5
Methanol permeability test
For the direct methanol fuel cell, the membrane was also required to have low methanol permeability, and methanol permeability of the oriented nanowire-shaped proton exchange membrane 2 (thickness of 49mm) and the Nafine-115 membrane (thickness of 125mm) were tested under the same conditions, and the values thereof were 0.707 x 10, respectively-7cm2·s-1And 1.27 x 10-6cm2·s-1It can be seen that the oriented proton exchange membrane has a lowerMethanol permeability, which is attributed to the introduced MOFs structure and the aligned nanowires can effectively inhibit the diffusion of methanol, in other words, MOFs help to capture methanol, resulting in high proton conductivity.
The polymer within the uniaxially aligned nanowires is strongly oriented in the axial direction of the nanowires, and may also promote phase separation in polymers having hydrophobic and hydrophilic domains. When a polymer having both hydrophobic and hydrophilic domains is electrically polled, its hydrophobic and hydrophilic domains may separate to the outside as the air surface and the interior of the polymer solution, respectively. Thus, due to the network of sulfonamide and triazole rings, proton channel structures are formed within the nanowires, resulting in rapid transport of protons within the proton transport sites, as shown in fig. 10.
Referring to FIG. 10, triazole rings and PES-SO in MOFs during the formation of nanowire films2Hydrophilic attraction between sulfonamide groups in Cl causes ionic clusters, which may contain proton groups from sulfonamide and Atz, to be aggregated inside. Compared with sulfonic acid, sulfonimide is a stronger acid, and can easily generate protons at high temperature, and the protons migrate from the polymer to the MOFs, transfer to the surface of the MOFs through hydrogen bonds, and then diffuse to the next MOFs through the structure to form a complete proton conduction route, namely a hopping mechanism followed by proton transmission. Thus, the added internal proton groups form long-distance proton transport paths along the nanowires, ensuring efficient transport of protons through the entire membrane.
The dark areas in b of fig. 10 represent hydrophilic domains and the light areas represent hydrophobic domains, and therefore the nanowires contain a large number of hydrophilic groups, which also allow efficient proton transport within the nanowires.
We believe that tautomerization and intramolecular proton transfer of Atz in MOFs in the membrane may also play an important role in the proton conduction process. It is reported that Atz-based systems have advantages in proton transfer due to the presence of multiple tautomers of triazole, which would reduce the number of conformational changes required. Atz can be viewed as a scaffold that can provide proton conducting channels in two modes simultaneously, as shown in fig. 11.
In summary, the oriented MOFs-SPES composite proton exchange membrane contains a uniaxial orientation MOFs-SPES nanowire structure, and can realize high proton conductivity, low methanol permeability and good chemical and thermal stability under high temperature and anhydrous conditions.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A metal organic framework material is characterized in that the molecular formula is (NH)4)4[TcMo2(OX)6(Atz)2]3Wherein OX is oxalic acid, and Atz is 3-amino-1, 2, 4-triazole.
2. A method for preparing a metal organic framework material according to claim 1, comprising the following steps:
dissolving oxalic acid, 3-amino-1, 2, 4-triazole, ammonium permanganate, soluble technetium salt and soluble molybdenum salt in a solvent to obtain a reaction solution;
and placing the reaction solution in a closed space for solvothermal reaction to obtain the metal organic framework material.
3. A proton exchange membrane is characterized by comprising a polymer substrate and a metal organic framework material dispersed in the polymer substrate, wherein the molecular formula of the metal organic framework material is (NH)4)4[TcMo2(OX)6(Atz)2]3Wherein OX is oxalic acid, and Atz is 3-amino-1, 2, 4-triazole.
4. The proton exchange membrane according to claim 3, wherein the metal organic framework material is oriented.
5. The proton exchange membrane according to claim 4, wherein the polymer substrate comprises an aromatic ring structure or an aromatic heterocyclic structure, and the aromatic ring structure or the aromatic heterocyclic structure is aligned with the metal-organic framework material.
6. The proton exchange membrane according to claim 4, wherein the mass of the metal organic framework material accounts for 10% to 50% of the total mass of the proton exchange membrane;
the polymer substrate is polyether sulfone containing chlorosulfonic acid groups.
7. A preparation method of a proton exchange membrane is characterized by comprising the following steps:
providing a slurry of a polymeric substrate;
providing a metal organic framework material having a molecular formula of (NH)4)4[TcMo2(OX)6(Atz)2]3Wherein OX is oxalic acid, and Atz is 3-amino-1, 2, 4-triazole;
dispersing the metal organic framework material in the slurry of the polymer substrate to obtain the slurry of the proton exchange membrane, and curing the slurry of the proton exchange membrane to obtain the proton exchange membrane.
8. The method for preparing the proton exchange membrane according to claim 7, wherein an electric field is applied to the slurry of the proton exchange membrane when the slurry of the proton exchange membrane is solidified, and the metal organic framework material is aligned under the action of the electric field.
9. The method for preparing a proton exchange membrane according to claim 8, wherein after the curing the slurry of the proton exchange membrane, the method further comprises: hot-pressing the proton exchange membrane;
the strength of the electric field is 20 kV/m-80 kV/m.
10. A fuel cell comprising the proton exchange membrane according to any one of claims 3 to 6.
CN202110844699.XA 2021-07-26 2021-07-26 Metal organic framework material and preparation method thereof, proton exchange membrane and preparation method thereof, and fuel cell Withdrawn CN113527705A (en)

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Citations (3)

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CN103779597A (en) * 2014-03-04 2014-05-07 中国科学技术大学 Method for preparing high-temperature proton exchange membrane
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CN103779597A (en) * 2014-03-04 2014-05-07 中国科学技术大学 Method for preparing high-temperature proton exchange membrane
CN106279221A (en) * 2016-07-13 2017-01-04 南京工业大学 Synthesis method of high-proton conductive metal organic framework material
CN108841008A (en) * 2018-06-27 2018-11-20 首都师范大学 A kind of preparation of the Solid-State proton conductive material with wide operating temperature range

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