CN111592660A - One-dimensional coordination polymer of nickel, preparation method thereof and application thereof in proton conducting membrane of fuel cell - Google Patents
One-dimensional coordination polymer of nickel, preparation method thereof and application thereof in proton conducting membrane of fuel cell Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a nickel one-dimensional coordination polymer, a preparation method thereof and application thereof in a fuel cell proton conducting membrane, wherein the structural formula of the coordination polymer is as follows: [ (Ni)2L(H2O)3)·3H2O] n (1) Belongs to the monoclinic system, and belongs to the monoclinic system,P2(1)/cthe space group, the molecular chain of the coordination polymer is distributed along the direction of the b axis vertical to the ac surface, no hydrogen bond path is formed along the direction of the b axis of the one-dimensional chain of the molecule, and stable, complex and various hydrogen bond networks are formed in a series of planes passing through the outer core Ni and parallel to the ac surface, and the networks form the proton conductivity of the complex. The polymer crystal sample has good stability, can keep the basic structure unchanged in the processes of soaking in water for one month, refluxing in boiling water for 20 hours, testing conductivity and the like, and has the advantages of relieving the faced energy exhaustion and developing and utilizing novel energyHas potential application value.
Description
Technical Field
The invention belongs to the field of functional complex chemistry, and particularly relates to a nickel one-dimensional coordination polymer, a preparation method thereof and application thereof in a fuel cell proton conducting membrane.
Background
Fuel Cells (FCs), which are highly efficient electrochemical power generation devices, have been considered as the primary energy source for widespread use. Hydrogen-oxygen fuel cells are favored as a non-polluting, clean-type power generation device because of their high energy density and high energy conversion efficiency. The working principle of the battery is as follows: oxygen is used as an anode, hydrogen is used as a cathode, electrons of the hydrogen are lost on the cathode, the hydrogen flows into the anode through an external circuit, and cation hydrogen passes through a proton exchange membrane to be combined with the oxygen on the anode to generate water, namely the hydrogen and the oxygen in the proton exchange membrane fuel cell are combined to generate water and generate electric energy.
The performance of pem fuel cells depends primarily on the proton conduction rate, for which great efforts have been made. Of the many studies, Nafion proton exchange membranes developed by dupont are the most widely used and successful. However, such membranes are very costly and poorly temperature-adaptable (less than 80 ℃) making their use very limited on a large scale. Nowadays, the energy is increasingly tense, and a proton exchange membrane which is cheap, has strong temperature adaptability and good performance is very urgent.
The proton conductivity research of MOFs is developed aiming at the defects of a Nafion proton exchange membrane. It is a material which is most likely to become a cheap and excellent proton conducting membrane in the future. This is because: the material not only has the structural characteristics of larger specific surface area, porosity and high extensibility, but also has the characteristics of structural adjustability, chemical stability, easiness in assembly, easiness in use in combination with other materials and the like, so that the material has inherent advantages in the aspect of selecting proton conducting membrane materials.
Currently, the research on the proton conductivity of MOFs is mainly focused on high-dimensional coordination polymers with porous structures, especially hydrophilic pores. The substances are easy to adsorb water molecules, carboxylic acid groups and other organic and inorganic groups capable of forming potential hydrogen bonds, and hydrogen bond paths are formed in holes, so that the proton conduction function is achieved, and the expected purpose is achieved.
Proton conduction is mainly based on two mechanisms, the Grotthus mechanism and the Vehicular mechanism. The grotthus mechanism is a proton conduction mode built on an infinite hydrogen bond network. Through hydrogen bonding, protons are transported between water molecules, and adjacent water molecules are connected with each other to form a continuous proton transfer channel. That is, proton transfer relies on hydrogen bonding. The Vehicular mechanism is aided by a carrier (e.g., H)2O、NH3) Then, the proton conduction is completed with the movement of the carrier. Two different conduction mechanisms can generally be distinguished by activation energy. Since the grotthus mechanism is due to the splitting of hydrogen bonds (close to 0.11eV), its activation energy (Ea) tends to be lower than 0.4 eV; in conduction of the Vehicular mechanism, the vector (H) is transferred3O+、NH4 +) More energy is required, and the activation energy (Ea) is generally higher than 0.4 eV.
The reason why a substance conducts electricity is that charged particles which can move freely exist in the substance. Thus, the proton conductivity of MOFs should benefit from the ability to form hydrogen bonding pathways within their structure that serve to conduct protons, rather than the presence of channels that accommodate hydrophilic groups. According to this thinking, when studying the proton conductivity of MOFs, the material selection is limited to high dimension and holes, which is not very scientific. On the contrary, a one-dimensional, two-dimensional, low-dimensional coordination polymer containing N, O, F coordination atom ligands which are liable to form hydrogen bonds may be more favorable for forming a stable hydrogen bond conduction path, thereby playing a role in proton conduction and electrical conductivity.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nickel one-dimensional coordination polymer, a preparation method thereof and application thereof in a fuel cell proton conducting membrane. Meanwhile, the one-dimensional Schiff base coordination polymer (3D supermolecule constructed by a hydrogen bond network) of nickel with proton conductivity can be used as a proton conducting material by depending on a conduction mechanism of the hydrogen bond network for conducting protons.
In order to solve the technical problems, the invention adopts the following technical scheme:
the one-dimensional coordination polymer of nickel has a structural formula as follows: [ (Ni)2L(H2O)3)·3H2O]n(1) Belonging to monoclinic system, P2(1)/c space group, wherein the ligand of the complex-glycine dipeptide 3-aldehyde 4-hydroxybenzoic acid (H)4L) the structural simple formula is:
further, the molecular chains of the coordination polymer are distributed along the b-axis direction perpendicular to the ac surface.
Furthermore, the molecular chain of the coordination polymer has no hydrogen bond path along the direction of the b axis and has no proton conduction performance; and in a series of planes passing through the outer core Ni and parallel to the ac surface, stable, complex and various hydrogen bond networks are formed to form a proton conduction path.
Further, the conduction mechanism of the coordination polymer for conducting protons by means of a hydrogen bond network should be the grotthus mechanism.
Further, the preparation method of the nickel one-dimensional coordination polymer comprises the following steps: at a concentration of 0.01 mol. L-1-0.1mol·L-1H of (A) to (B)4Adding Ni (NO) into L methanol aqueous solution3)2·6H2O and LiOH H2And O, keeping the temperature of the mixture at the temperature of between 80 and 110 ℃ for 72 hours, and naturally cooling the mixture to obtain blue single crystals, namely the nickel one-dimensional coordination polymer.
Further, said Ni (NO)3)2·6H2The amount of O substance is H42 times the amount of substance L, said LiOH H2The amount of O substance is H44 times the amount of substance L.
Further, the volume ratio of methanol to water in the methanol aqueous solution is 1: 1.
The conductivity of the complex 1 is closely related to humidity and temperature, the conductivity is enhanced along with the increase of the humidity and the temperature, and the complex can work from 50 ℃ to 100 ℃ (shown in figures 4-9), wherein the influence of the temperature is more remarkable, for example, at 50 ℃, RH is 68% and 100%, the molar conductivity sigma is 7.7030 × 10-5S·cm-1Increased to 8.9128 × 10-5S·cm-1At 68% RH, 50-100 deg.C, and the molar conductivity sigma is 7.7030 × 10-5S·cm-1Increased to 3.7398 × 10- 4S·cm-1Increasing nearly 6 times, and at 100% RH, from 50 deg.C to 100 deg.C, the molar conductivity sigma is 8.9128 × 10-5S·cm-1Increased to 3.1281 × 10-4S·cm-1The increase is nearly 4 times. This can be reasonably explained from the fact that the complex is relatively stable, water molecules are not easy to lose at 100 ℃, and internal hydrogen bonds can stably exist (figure 2).
The complex 1 is a 3D supermolecule network extended from a one-dimensional chain structure through hydrogen bond action. No hydrogen bond path is formed in the molecular chain along the direction of the b axis, and the proton conduction performance is not realized in the direction; and in a series of planes passing through the outer core Ni of the structural unit and parallel to the ac coordinate plane, stable, complex and various hydrogen bond networks are formed to form a proton conduction path. Thus, the complex shows a distinct anisotropic proton conduction characteristic (as shown in fig. 1).
The activation energy (Ea) of complex 1 at 68%, 75%, 93% and 100% RH, fitted according to the arrhenius equation, is 0.36eV, 0.27eV, 0.26eV and 0.20eV, respectively, all less than 0.4eV, and therefore the proton conduction mechanism should be the grotthus mechanism. Shows that the movement of protons is established on an infinite hydrogen bond network, and does not depend on the help of carriers (such as H)2O、NH3) The proton is conducted with the movement of the carrier. This can be reasonably explained from the experimental fact that one-dimensional chains exhibiting non-porous, close parallel arrangement are extended into 3D supramolecular structures by hydrogen bonding networks (see fig. 1)Shown in fig. 10-13).
The hydrogen bond between the 1-chain of the complex not only can extend the one-dimensional complex molecule with a chain structure into a 3D supermolecule network, but also can form a stable, complex and various hydrogen bond network in the crystal. The network is formed on the basis of enough short distance between molecular chains, and if the distance between the molecular chains is enlarged, the difficulty of forming hydrogen bonds is increased, and the construction of the hydrogen bonds is extremely unfavorable. Therefore, the parallel close arrangement of the one-dimensional chain molecules which conduct protons by means of the hydrogen bond network is beneficial to the enhancement of the proton conducting capability of the complex (as shown in FIG. 1).
The invention has the beneficial effects that:
1. the polymer crystal sample has good stability, and can keep the basic structure unchanged in the processes of soaking in water for one month, refluxing in boiling water for 20 hours, conducting property testing, and the like. The proton conductivity experiment shows that: the compound has different proton conductivity under different humidity and temperature conditions, the strength of the conductivity has larger dependence on temperature and humidity, and the influence of temperature is larger. The Aloneius formula fitting shows that the activation energy (Ea) is less than 0.4eV at 68%, 75%, 93% and 100% RH, which indicates that the movement of protons is established on an infinite hydrogen bond network and belongs to the Grotthus mechanism.
2. Displaying a three-dimensional supermolecular structure: no hydrogen bond path is formed along the direction of the b axis of the molecular one-dimensional chain, and stable, complex and various hydrogen bond networks are formed in a series of planes which pass through the outer core Ni and are parallel to the ac plane, the networks form the proton conductivity of the complex, and the close and parallel arrangement of the one-dimensional molecular chains can strengthen the hydrogen bond networks, so that the proton conductivity of the complex is enhanced.
Drawings
FIG. 1(a) the asymmetric unit of the complex and the coordination environment of Ni; (b) the complex molecule forms a 1D chain along the b axis; (c) three-dimensional supramolecules (no hydrogen bonding path formed along the b-axis direction) constructed by interchain hydrogen bonds; (d) a hydrogen bond pathway formed in a plane passing through the outer core Ni and parallel to the ac coordinate plane; (e) a hydrogen bonding pathway schematic without lattice water molecules participating;
FIG. 2 is a thermogravimetric analysis diagram of the complex 1, in which the complex does not lose water within 100 ℃, loses crystal water at 100-150 ℃, removes the coordination water after 150 ℃, and the framework begins to collapse and decompose at 400 ℃;
FIG. 3 simulates the XRD pattern of a single crystal sample and the sample test XRD patterns of 68% RH, 100% RH, 93% RH;
FIG. 4a is a Nyquist plot of complex 1 at different temperatures of 53% RH (b is a Nyquist plot at 50 ℃, 60 ℃, c is 70 ℃, 80 ℃, d is 90 ℃, 100 ℃ after amplification);
FIG. 5a is a Nyquist plot of complex 1 at different temperatures of 68% RH (b is a Nyquist plot at 50 ℃, 60 ℃, c is 70 ℃, 80 ℃, d is 90 ℃ and 100 ℃ C. after amplification);
FIG. 6a is a Nyquist plot of complex 1 at different temperatures of 75% RH (b is a Nyquist plot at 50 ℃, 60 ℃, c is 70 ℃, 80 ℃, d is 90 ℃, 100 ℃ after amplification);
FIG. 7 is a Nyquist plot of complex 1 at different temperatures of 85% RH (Nyquist plots of 40 ℃ C., 50 ℃ C., 60 ℃ C., 70 ℃ C., 80 ℃ C., 90 ℃ C., 100 ℃ C.);
FIG. 8a is a Nyquist plot of complex 1 at various temperatures of 93% RH (b is a Nyquist plot at 50 ℃, 60 ℃, c is 70 ℃, 80 ℃, d is 90 ℃, 100 ℃ C. after amplification);
FIG. 9a is a Nyquist plot of complex 1 at different temperatures of 100% RH (b is a Nyquist plot at 50 ℃, 60 ℃, c is 70 ℃, 80 ℃, d is 90 ℃, and 100 ℃ C. after amplification);
FIG. 10 Allen-baus fit of complex 1 at 68% RH;
FIG. 11 Allen-baus fit of complex 1 at 75% RH;
FIG. 12 Allnius fit plot of complex 1 at 93% RH;
FIG. 13 Arrhenius fit of complex 1 at 100% RH.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The preparation method of the nickel one-dimensional coordination polymer of the embodiment is as follows:
step 1, preparation of glycine dipeptide 3-aldehyde 4-hydroxybenzoic acid: 0.2641g (2mmol) of glycine dipeptide was weighed out and dissolved in 20mL of water, and the solution was put into a three-necked flask having a capacity of 150mL, and heated to 80 ℃. Then under magnetic stirring, adding 0.3340g (2mmol) of 3-formyl 4-hydroxybenzoic acid dissolved in 20mL of methanol solution into the solution, stirring for 2 hours at constant temperature, naturally cooling, rotary evaporating, and recrystallizing with 1:4 methanol aqueous solution to obtain ligand H4L (molecular formula: C)12H12N2O6) The yield was 55%.
Step 2, preparing Ni complex single crystal: 0.0140g (0.05mmol) of ligand H was weighed4L、0.0290g(0.10mmol)Ni(NO3)2·6H2O、0.0084g(0.20mmol)LiOH·H2And O, adding the mixture into a small glass bottle with the capacity of 15mL and containing 5mL of 1:1 methanol aqueous solution, uniformly mixing, putting the mixture into a steel bottle with a polytetrafluoroethylene lining, keeping the temperature of the steel bottle constant at 80 ℃ for 72 hours, and naturally cooling to obtain blue crystals, namely the single crystals of the target complex, wherein the yield is 70%. The structural formula of the complex is as follows: [ (Ni)2L(H2O)3)·3H2O]n(1) The molecular formula is: c12H20N2Ni2O12Belongs to monoclinic system, P2(1)/c space group. The coordination environment of nickel is shown in figure 1a, the structure of polymer 1D is shown in figure 1b, and the hydrogen bonding network is shown in figures 1c-1 e.
The single crystal has different proton conductivity under different humidity and temperature conditions, and the dependence of the conductivity on the temperature and the humidity is larger. The activation energy was less than 0.4ev under the conditions of 68%, 75%, 93% and 100% RH according to the arrhenius equation fitting, so the conduction mechanism should be the grotthus mechanism, as shown in fig. 10-13.
According to thermogravimetric analysis, the complex does not lose water within 100 ℃, loses crystal water at 100-150 ℃, and begins to remove coordinated water after 150 ℃. However, in this process, the structure of the complex can still be stable, and the skeleton does not collapse until 400 ℃, and the complex starts to decompose, as shown in FIG. 2.
PXRD research of the complex shows that the basic structure of the complex can be kept unchanged in the processes of soaking the complex in water for one week, refluxing in boiling water for 24 hours, dehydration before skeleton collapse at high temperature, conducting performance test, re-water absorption after complex dehydration and the like, as shown in figure 3.
The conduction mechanism of the complex is as follows: the proton conduction of the complex 1 can be completed by a hydrogen bond network in supermolecule, a proton channel is formed through the hydrogen bond network, and protons are transmitted along an ac surface, so that the proton conduction performance is realized. As shown in fig. 10-13.
Example 2
The preparation method of the nickel one-dimensional coordination polymer of the embodiment is as follows:
step 1, preparation of glycine dipeptide 3-aldehyde 4-hydroxybenzoic acid: 0.5282g (4mmol) of glycine dipeptide was weighed out and dissolved in 30mL of water, and the solution was put into a three-necked flask having a capacity of 250mL, and heated to 80 ℃. Then under magnetic stirring, adding 0.6680g (4mmol) of 3-formyl 4-hydroxybenzoic acid dissolved in 30mL of methanol solution into the solution, stirring for 4 hours at constant temperature, naturally cooling, rotary evaporating, and recrystallizing with 1:4 methanol aqueous solution to obtain ligand H4L (molecular formula: C)12H12N2O6) The yield was 50%.
Step 2, preparing Ni complex single crystal: 0.0280g (0.10mmol) of ligand H is weighed4L、0.0580g(0.20mmol)Ni(NO3)2·6H2O、0.0168g(0.40mmol)LiOH·H2O, adding into a small glass bottle with the capacity of 15mL containing 7mL of 1:1 methanol aqueous solution, uniformly mixing, placing into a steel bottle with a polytetrafluoroethylene lining, keeping the temperature at 110 ℃ for 72 hours, and naturally cooling to obtain blue crystals, namely the target compoundSingle crystal of substance, yield 65%.
The main crystallographic data of the complex are shown in table 1, and the bond length angle of part of the complex is shown in table 2.
TABLE 1 crystallographic data for the complexes
TABLE 2 partial bond Length bond angles of the complexes
Symmetry codes:#3:1-x,-y,1-z
The above examples are merely illustrative of the present invention, and other embodiments of the present invention are possible. However, all the technical solutions formed by equivalent alternatives or equivalent modifications fall within the protection scope of the present invention.
Claims (10)
1. A one-dimensional coordination polymer of nickel characterized by: the structural formula of the coordination polymer is as follows: [ (Ni)2L(H2O)3)·3H2O] n (1) Belongs to the monoclinic system, and belongs to the monoclinic system,P2(1)/cspace group, in which the ligand of the complex-glycine dipeptide 3-aldehyde 4-hydroxybenzoic acid (H)4L) the structural formula is:
2. the one-dimensional coordination polymer of nickel of claim 1, characterized in that: the molecular chains of the coordination polymer are distributed along the direction of a b axis vertical to an ac surface.
3. The one-dimensional coordination polymer of nickel of claim 2, characterized in that: the molecular chain of the coordination polymer has no hydrogen bond path along the direction of the b axis and has no proton conduction performance; and in a series of planes passing through the outer core Ni and parallel to the ac surface, stable, complex and various hydrogen bond networks are formed to form a proton conduction path.
4. The one-dimensional coordination polymer of nickel of claim 3, characterized in that: the conduction mechanism of the coordination polymer for conducting protons by means of a hydrogen bond network should be the Grotthus mechanism.
5. The method for producing a one-dimensional coordination polymer of nickel according to claim 1, characterized by comprising the steps of: at a concentration of 0.01 mol. L-1-0.1mol·L-1H of (A) to (B)4Adding Ni (NO) into L methanol aqueous solution3)2·6H2O and LiOH H2O, at 80oC-110oAnd C, keeping the temperature for 72 hours, and naturally cooling to obtain a blue single crystal, namely the nickel one-dimensional coordination polymer.
6. The method for producing a one-dimensional coordination polymer of nickel according to claim 5, characterized in that: the Ni (NO)3)2·6H2The amount of O substance is H42 times the amount of substance L, said LiOH H2The amount of O substance is H44 times the amount of substance L.
7. The method for producing a one-dimensional coordination polymer of nickel according to claim 5, characterized in that: the volume ratio of methanol to water in the methanol aqueous solution is 1: 1.
8. Use of a one-dimensional coordination polymer of nickel according to claim 1, characterized in that: the one-dimensional coordination polymer of nickel is used as a proton conducting material for manufacturing a proton conducting membrane of a fuel cell.
9. Use according to claim 8, characterized in that: the working temperature of the one-dimensional coordination polymer of nickel is 50-100 ℃.
10. Use according to claim 8, characterized in that: the conductivity of the nickel one-dimensional coordination polymer is closely related to humidity and temperature, the conductivity is enhanced along with the increase of the humidity and the temperature, and the influence of the temperature on the conductivity is more obvious.
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