CN115521474B - Organic framework material based on five-fold interpenetrating hydrogen bonds and preparation method and application thereof - Google Patents
Organic framework material based on five-fold interpenetrating hydrogen bonds and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of preparation of hydrogen bond organic frame materials, and relates to a quintuple interpenetrating hydrogen bond organic frame material, which has the chemical formula: { (TSM) & 2 (DBPy) & 2 (H) 2 O) } n, n is a positive integer, TSM is a tetrakis (4-sulfophenyl) methane anion, DBPy is a 1,1 '-diamino-4, 4' -bipyridine cation; DBPy 2+ Amino group on TSM 4‑ The sulfonic group and the free water molecules interact to form a 3D honeycomb type framework, and three unique channels C1, C2 and C3 are arranged in the 3D honeycomb type framework; c1 is a quadrilateral channel, covered by a first type of TSM 4‑ Ligand occupation; c2 is a cross-shaped channel, covered by a second type of TSM 4‑ Ligand occupation; c3 is a rectangular channel, DBpy 2+ Ligand occupation; solves the problem that the existing hydrogen bond organic frame is easy to collapse.
Description
Technical Field
The invention belongs to the field of preparation of hydrogen bond organic frame materials, and particularly relates to a quintuple interpenetrating hydrogen bond organic frame material, a preparation method and application thereof.
Background
Hydrogen bonded organic frameworks (HOFs) have evolved into a unique class of crystalline porous materials, which are generally framework materials formed from organic or metal-organic building blocks interconnected by intermolecular hydrogen bonds. HOFs have their own characteristics, such as mild synthesis conditions, high crystallinity, solvent processability, ease of repair and regeneration, etc., compared to other crystalline porous materials containing organic components, such as metal-organic frameworks (MOFs) and Covalent Organic Frameworks (COFs). These characteristics of HOFs can make them a unique class of functional porous materials. Since it does not contain heavy metal ions, a more environmentally friendly solution is provided. Hydrogen bond organic frameworks (HOFs) have shown abundant application values in energy gas storage, selective separation, catalysis, small molecule recognition, proton conduction and other aspects, and have been a research hotspot in international academy in recent years. From a structural point of view, the building blocks and hydrogen bonding in HOFs make them ideal conductive materials. In particular, the hydrogen bond donor/acceptor groups of building blocks can be used as proton sources or carriers, while a wide range of hydrogen bonds provide a variety of proton transport pathways. And the most prominent feature is the solution processibility of HOFs, which opens up new possibilities for composite membrane fabrication.
The framework of most HOFs collapses relatively easily due to weak hydrogen bond strength and strong flexibility. However, HOF materials constructed mainly by supermolecule weak action such as hydrogen bond and pi-pi accumulation have poor stability, and severely restrict the application and development of the HOF materials.
Due to the upgrade of energy demands and the rising price of fossil fuels, new alternative energy sources are being investigated, and fuel cells are becoming an option. Among the many classifications of fuel cells, direct Methanol Fuel Cells (DMFCs) capable of directly converting chemical energy into electrical energy have been attracting attention because of their high energy efficiency, low pollutant emissions, long operating time, convenient fuel supply, and the like. Proton Exchange Membranes (PEM) prepared from HOFs serve as an important component of a fuel cell, functioning as both a proton conductor and a barrier to fuel permeation. However, the performance of the proton exchange membrane is also affected due to the problems of the HOFs material itself.
Disclosure of Invention
The invention aims to provide a quintuple interpenetrating hydrogen bond-based organic framework material, a preparation method and application thereof, and solves the problem that the existing hydrogen bond organic framework is easy to collapse.
The invention is realized by the following technical scheme:
an organic framework material based on a quintuple interpenetrating hydrogen bond has a chemical formula as follows: { (TSM) & 2 (DBPy) & 2 (H) 2 O) n, where n is a positive integer, TSM is a tetra (4-sulfophenyl) methane anion of the formula { TSM } 4- DBPy is 1,1 '-diamino-4, 4' -bipyridine cation,chemical formula is { C 10 H 12 N 4 } 2+ ；
DBPy 2+ Amino group on TSM 4- The sulfonic group and the free water molecules interact to form a 3D honeycomb type framework, and three unique channels are formed in the 3D honeycomb type framework and are named as C1, C2 and C3 respectively;
c1 is a quadrilateral channel, covered by a first type of TSM 4- Ligand occupation; c2 is a cross-shaped channel, covered by a second type of TSM 4- Ligand occupation; c3 is a rectangular channel, DBpy 2+ Ligand occupation;
TSM of the first type 4- The ligand is composed of a TSM 4- Sulfonic acid group and three 1/2 DBpy 2+ Is formed by hydrogen bonding;
TSM of the second type 4- The ligand is composed of a TSM 4- Sulfonic acid group and two 1/2 DBpy 2+ Is formed by hydrogen bonding;
the structural unit of the organic framework material based on the quintuple interpenetrating hydrogen bond belongs to a tetragonal system.
Further, the space group based on the quintuple interpenetrating hydrogen bond organic framework material is I-4, and the molecular formula is C 45 H 44 N 8 O 14 S 4 Unit cell parameters:α＝90.00°，β＝90.00°，γ＝90.00°，/>
further, the organic framework material based on the five-fold interpenetrating hydrogen bond is formed by polymerizing a plurality of repeating units, and each repeating unit comprises one TSM 4- Two DBPy 2+ And two water molecules.
Further, the organic framework material based on the five-fold interpenetrating hydrogen bonds is a porous material, and the temperature of thermal stability reaches 280 ℃.
Further, the organic framework material based on the five-fold interpenetrating hydrogen bonds has the humidity of 98 percentAnd proton conductivity at 100℃of 1.21X 10 -2 S·cm -1 ，E a ＝0.855eV。
The invention also discloses a preparation method of the organic framework material based on the quintuple interpenetrating hydrogen bond, which comprises the following steps:
1) Preparation of H 4 TSM ligand powder, H 4 The TSM ligand powder is completely dissolved in methanol to give H 4 TSM solution; completely dissolving DBpy.2I ligand in water to obtain DBPy.2I solution;
wherein H is 4 The molar ratio of TSM ligand to DBPy.2I ligand is (1-2): (2-5), wherein the molar ratio of the methanol to the water is (1-2), namely (1-2);
3) Mixing the two solutions at room temperature, and standing to obtain pale yellow transparent crystals, thus obtaining the organic frame material based on the five-fold interpenetrating hydrogen bonds.
Further, H 4 The preparation process of the TSM ligand powder comprises the following steps: at N 2 Adding tetraphenyl methane into dichloromethane under the atmosphere, dropwise adding chlorosulfonic acid under ice bath, filtering after reaction, washing with dichloromethane, filtering, recrystallizing with methanol to obtain H 4 TSM ligand powder.
The invention also discloses application of the organic framework material based on the quintuple interpenetrating hydrogen bond as a proton conductive material.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses an organic framework material based on five-fold interpenetrating hydrogen bonds, which is prepared from H 4 TSM ligand and DBPy.2I ligand are prepared, so H is selected 4 The TSM ligand is initially designed to have a macroporous hydrogen bond network structure, so that water molecules can enter and exit in a channel conveniently, and the proton conductivity of the TSM ligand is improved. The organic framework material based on the quintuple interpenetrating hydrogen bond is crystallized in the non-centrosymmetric tetragonal I-4 space group, which comprises two-fourth TSM 4- (from different TSMs) 4- Is a phenyl group-SO group 3- Radical), one DBpy 2+ A unit and a lattice water molecule (fig. 1 a). Generating the whole by symmetric operation according to the symmetry center and symmetry planeMultiple TSMs 4- A ligand. The whole structure is composed of TSM 4- Sulfonic acid anions of (C) and DBpy 2+ Part of aminopyridine cations and water molecules are connected through countless hydrogen bonds to form the 3D honeycomb type framework.
In addition, if aminopyridine cations in the structure are not considered, the sulfonic acid group anions and water molecules form a 3D honeycomb-type skeleton through hydrogen bonding interactions (fig. 2 a). Finally, DBpy 2+ The adjacent interpenetrating honeycomb structures are connected together by the amino group on the catalyst through N-H.O to generate a whole 3D ion hydrogen bond organic framework (figure 2 c), and the sulfonic group anions, aminopyridine cations and water molecules are assembled into a 3D electric neutral hydrogen bond network under the drive of the hydrogen bond. As shown in fig. 1, the remarkable characteristics of the material structure are as follows: a) An asymmetric unit of the material; b) For the first type of TSM 4- The method comprises the steps of carrying out a first treatment on the surface of the c) For the second type of TSM 4- The method comprises the steps of carrying out a first treatment on the surface of the d) Is DBpy 2+ Is connected with the connecting mode of the connecting device. As shown in fig. 4, the hydrogen bonding structure of this material reveals three unique channels: c1, C2 and C3 (fig. 4). C1 is a quadrilateral channel, covered by a first TSM 4- Ligand occupancy. C2 is a cross-shaped channel, surrounded by a second type of TSM 4- Ligand occupancy. C3 is a very small rectangular channel, DBpy 2+ Part of aminopyridine occupies part, and is beneficial to the entry and exit of water molecules due to the diversity of the channels and the existence of macropores in the channels, so that the proton conductivity is improved. The invention prepares the stable and porous HOF material by reasonably selecting the construction units with rigidity and specific geometric configuration and introducing quintuple interpenetration and pi-pi stacking action. The organic framework material based on the five-element interpenetrating hydrogen bonds, which is prepared by the invention, has good thermal stability, the XRD powder diffraction analysis data shows that the obtained product has higher purity, the thermogravimetric analysis shows that the thermal stability is high, the decomposition temperature of the three-dimensional porous framework is 280 ℃, and the organic framework material has better proton conductivity, and is a novel proton conductive material.
The five-fold inter-penetrating hydrogen bond organic framework material is characterized in that a 3D honeycomb type framework is formed between sulfonic anions and water molecules through hydrogen bond interaction under the condition of not considering aminopyridine cations in the structure, and then five identical honeycombs are formedThe inter-penetrating framework structure forms a hydrogen bond organic framework material with five-fold penetrating (figure 2 a), and when aminopyridine cations are added into the structure, DBpy 2+ The amino groups on the two groups connect adjacent interpenetrating honeycomb structures together through N-H.cndot.O to generate the whole 3D ion hydrogen bond organic framework (figure 2 c).
The proton exchange membrane material prepared by the invention based on the quintuple interpenetrating hydrogen bond organic framework material and Nafion solution through a recasting method has 72mW/cm 2 Is 1.4 times that of Nafion, and has a maximum current density of 432.6mA/cm 2 The ratio is improved by 1.3 times compared with Nafion. Therefore, the method has good application prospect in the methanol fuel cell.
The invention also discloses a preparation method of the organic framework material based on the quintuple interpenetrating hydrogen bond, which is formed by H 4 The TSM ligand and DBPy.2I ligand are prepared, the synthetic raw materials are obtained through an organic synthetic reaction, the preparation process is simple, the operation is convenient, and the yield is high. When the organic framework material based on the five-element interpenetrating hydrogen bond is used as a proton conducting material with a macroporous hydrogen bond network structure, the maximum conductivity can reach 2.1 multiplied by 10 -2 S·cm -1 Has good application prospect.
Drawings
FIG. 1 is an asymmetric unit diagram and ligand structure diagram of a hydrogen bonded organic framework material synthesized in accordance with the present invention; a) An asymmetric unit of the material; b) For the first type of TSM 4- The method comprises the steps of carrying out a first treatment on the surface of the c) For the second type of TSM 4- The method comprises the steps of carrying out a first treatment on the surface of the d) Is DBpy 2+ Is connected with the connecting mode of the connecting device;
FIG. 2 shows a TSM synthesized according to the present invention 4- And interpenetrating structures of water molecules and DBpy 2+ Distribution patterns in the interpenetration structure;
FIG. 3 is a schematic diagram of the supramolecular structure of the hydrogen bonded organic framework material synthesized in the present invention;
FIG. 4 is a graph of hydrogen bond network and a graph of hydrogen bond network channels for hydrogen bond organic framework materials synthesized in accordance with the present invention; FIG. a is a hydrogen bond network diagram of a hydrogen bond organic framework material synthesized in accordance with the present invention; FIG. b is a graph of hydrogen bond network channel distribution of the hydrogen bond organic framework material synthesized in accordance with the present invention;
FIG. 5 is a graph showing the measured PXRD and simulated PXRD of the hydrogen bonded organic framework material crystals synthesized in example 3 of the present invention;
FIG. 6 is a thermogravimetric analysis of crystals of hydrogen bonded organic framework materials synthesized in example 3 of the present invention;
FIG. 7 is a graph showing the impedance of the hydrogen bonded organic framework material synthesized in example 3 of the present invention;
FIG. 8 is an analysis chart of the activation energy of the hydrogen bond organic framework material synthesized in example 3 of the present invention;
FIG. 9 is an electrochemical impedance diagram of the proton exchange membrane material prepared in example 7 of the present invention;
fig. 10 is a graph showing the performance of a fuel cell of the proton exchange membrane material prepared in example 7 of the present invention.
Detailed Description
The objects, technical solutions and advantages of the present invention will be more apparent from the following detailed description with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention.
The components illustrated in the figures and described and shown in the embodiments of the invention may be arranged and designed in a wide variety of different configurations, and thus the detailed description of the embodiments of the invention provided in the figures below is not intended to limit the scope of the invention as claimed, but is merely representative of selected ones of the embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention, based on the figures and embodiments of the present invention.
The features and properties of the present invention are described in further detail below with reference to examples.
The invention discloses an organic framework material based on five-fold interpenetrating hydrogen bonds, which has the chemical formula: { (TSM) & 2 (DBPy) & 2 (H) 2 O) n, where n is a positive integer, TSM is a tetra (4-sulfophenyl) methane anion of the formula { TSM } 4- DBPy is 1,1 '-diamino-4, 4' -)Bipyridine cations with a chemical formula of { C 10 H 12 N 4 } 2+ 。
The invention also discloses a preparation method of the organic framework material based on the five-fold interpenetrating hydrogen bond, which comprises the following steps:
1) Preparation of H 4 TSM ligand powder;
2) Will H 4 The TSM ligand powder is completely dissolved in methanol to give H 4 TSM solution;
completely dissolving 1,1 '-diamino-4, 4' -bipyridine diiodide (DBpy.2I) in water to obtain DBPy.2I solution;
wherein H is 4 The molar ratio of TSM ligand to DBPy.2I ligand is (1-2): (2-5), wherein the molar ratio of the methanol to the water is (1-2), namely (1-2);
3) The two solutions are mixed at room temperature and then are stood still to obtain pale yellow transparent crystals.
The invention is described in further detail below with reference to examples:
example 1
The invention discloses a preparation method of an organic framework material based on five-fold interpenetrating hydrogen bonds, which comprises the following steps:
1) At N 2 Under the atmosphere, adding tetraphenyl methane into dichloromethane, dropwise adding chlorosulfonic acid (dropwise adding is completed in 1H) in an ice bath, continuously reacting for 3 hours, filtering, washing with dichloromethane, filtering, and recrystallizing with methanol to obtain H 4 TSM ligand powder.
2) Will H 4 TSM is completely dissolved in methanol to give H 4 TSM solution; completely dissolving 1,1 '-diamino-4, 4' -bipyridine diiodide (DBpy.2I) in water to obtain DBPy.2I solution;
wherein H is 4 The molar ratio of TSM ligand to DBPy.2I ligand is 2:3, the molar ratio of methanol to water is 1:1;
3) The two solutions are mixed at room temperature and then are stood still to obtain pale yellow transparent crystals.
The yield of hydrogen bonded organic framework material obtained in this example was 65%.
Example 2
The invention discloses a preparation method of an organic framework material based on five-fold interpenetrating hydrogen bonds, which comprises the following steps:
1) At N 2 Under the atmosphere, adding tetraphenyl methane into dichloromethane, dropwise adding chlorosulfonic acid (dropwise adding is completed in 1H) in an ice bath, continuously reacting for 3 hours, filtering, washing with dichloromethane, filtering, and recrystallizing with methanol to obtain H 4 TSM ligand powder.
2) Will H 4 TSM is completely dissolved in methanol to give H 4 TSM solution; completely dissolving 1,1 '-diamino-4, 4' -bipyridine diiodide (DBpy.2I) in water to obtain DBPy.2I solution;
wherein H is 4 The molar ratio of TSM ligand to DBPy.2I ligand is 1:3, the molar ratio of methanol to water is 1:2;
3) The two solutions are mixed at room temperature and then are stood still to obtain pale yellow transparent crystals.
The yield of organic framework material based on five-fold interpenetrating hydrogen bonds obtained in this example was 70%.
Example 3
The invention discloses a preparation method of an organic framework material based on five-fold interpenetrating hydrogen bonds, which comprises the following steps:
1) At N 2 Under the atmosphere, adding tetraphenyl methane into dichloromethane, dropwise adding chlorosulfonic acid (dropwise adding is completed in 1H) in an ice bath, continuously reacting for 3 hours, filtering, washing with dichloromethane, filtering, and recrystallizing with methanol to obtain H 4 TSM ligand powder.
2) Will H 4 TSM is completely dissolved in methanol to give H 4 TSM solution; completely dissolving 1,1 '-diamino-4, 4' -bipyridine diiodide (DBpy.2I) in water to obtain DBPy.2I solution;
wherein H is 4 The molar ratio of TSM ligand to DBPy.2I ligand is 1:2, the molar ratio of methanol to water is 1:1;
3) The two solutions are mixed at room temperature and then are stood still to obtain pale yellow transparent crystals.
The yield of organic framework material based on five-fold interpenetrating hydrogen bonds obtained in this example was 75%.
Example 4
The invention discloses a preparation method of an organic framework material based on five-fold interpenetrating hydrogen bonds, which comprises the following steps:
at N 2 Under the atmosphere, adding tetraphenyl methane into dichloromethane, dropwise adding chlorosulfonic acid (dropwise adding is completed in 1H) in an ice bath, continuously reacting for 3 hours, filtering, washing with dichloromethane, filtering, and recrystallizing with methanol to obtain H 4 TSM ligand powder.
1) Will H 4 TSM is completely dissolved in methanol to give H 4 TSM solution; completely dissolving 1,1 '-diamino-4, 4' -bipyridine diiodide (DBpy.2I) in water to obtain DBPy.2I solution;
wherein H is 4 The molar ratio of TSM ligand to DBPy.2I ligand is 2:1, the molar ratio of methanol to water is 2:1;
2) The two solutions are mixed at room temperature and then are stood still to obtain pale yellow transparent crystals.
The yield of organic framework materials based on five-fold interpenetrating hydrogen bonds obtained in this example was 50%.
In the above embodiment, with the embodiment 3 as the best embodiment, the organic frame material based on the five-fold interpenetrating hydrogen bonds prepared in the embodiment 3 is subjected to monochromatization of Cu K alpha by a graphite monochromator on a Bruke smart APEXII CCD diffractometerRay, scan in omega-theta mode, collect diffraction point at 298K, correct structural analysis of F2 via full matrix least squares method is done with shelxl=2014 software package. The structural unit of the material belongs to tetragonal system, the space group is I-4, and the molecular formula is C 45 H 44 N 8 O 14 S 4 Unit cell parameters:α＝90.00°，β＝90.00°，γ＝90.00°，/>
the organic framework material based on the five-fold interpenetrating hydrogen bonds is formed by polymerizing a plurality of repeating units, and each repeating unit comprises a TSM 4- Two DBPy 2+ And two water molecules.
As shown in fig. 1, the remarkable characteristics of the material structure are as follows: a) An asymmetric unit of the material; b) For the first type of TSM 4- The method comprises the steps of carrying out a first treatment on the surface of the c) For the second type of TSM 4- The method comprises the steps of carrying out a first treatment on the surface of the d) Is DBpy 2+ Is connected with the connecting mode of the connecting device. The repeating units being asymmetric structural units, each repeating unit comprising a TSM 4- Two DBPy 2+ And two water molecules. DBPy 2+ Amino group on TSM 4- The sulfonic acid groups and the free water molecules form a three-dimensional hydrogen bond network with pore channels.
As shown in fig. 4a and 4b, there are three distinct channels in the hydrogen bond network of the material: c1, C2 and C3, C1 being a quadrilateral channel, is defined by a first TSM 4- Ligand occupation; c2 is a cross-shaped channel, surrounded by a second type of TSM 4- Ligand occupation; c3 is a very small rectangular channel, DBpy 2+ Ligand occupancy. The diversity of the channels and the existence of macropores in the channels are beneficial to the entry and exit of water molecules, so that the proton conductivity is improved.
As shown in fig. 5, the obtained powder diffraction data of the organic framework material powder sample based on the quintuple interpenetrating hydrogen bond and the obtained powder diffraction data of the single crystal are compared, and the obtained diffraction peak of the organic framework material based on the quintuple interpenetrating hydrogen bond is consistent with the peak simulated by the diffraction data of the X-single crystal, so that the purity of the obtained material powder sample is higher, and meanwhile, the experimental reproducibility of the sample is proved to be good.
As shown in fig. 6, thermal stability of the organic framework material based on the five-fold interpenetrating hydrogen bonds was obtained by thermogravimetric analysis. The three-dimensional structure of the obtained organic framework material based on the five-fold interpenetrating hydrogen bonds can be stabilized to 280 ℃ through a thermogravimetric analysis curve, and collapse occurs after the three-dimensional structure. The prepared material has good thermal stability, and is a new material with practical application value.
The invention is thatThe impedance of the organic framework material based on the five-element interpenetrating hydrogen bonds at 98 percent of humidity and 100 ℃ is shown as figure 7, and the proton conductivity of the material can reach 2.1 multiplied by 10 -2 S·cm -1 。
From the activation energy curve of FIG. 8, it can be seen that E a =0.885 eV, conforming to the vehicle mechanism.
In conclusion, the organic framework material based on the quintuple interpenetrating hydrogen bond synthesized by the invention has a three-dimensional porous hydrogen bond network, and the material has good thermal stability, can have good proton conductivity under the conditions of high temperature and high humidity, and has the proton conductivity reaching 2.1 multiplied by 10 at the temperature of 100 ℃ under the humidity of 98 percent -2 S·cm -1 。
The invention also discloses a preparation method of the proton exchange membrane material, which comprises the following steps:
1) 12mg of crystals were weighed, added to 2-3mL of isopropanol solution, and dispersed in ultrasound for 30min.
2) 1500mg of Nafion aqueous solution (10%) was weighed into 3mL of isopropanol and stirred well.
3) Dropwise adding 1) into 2), and continuously stirring for 4-8h.
4) Pouring the uniformly stirred liquid into a polytetrafluoroethylene mould, airing at room temperature, and carrying out post-treatment, namely taking the composite membrane.
Example 5
The invention discloses a preparation method of a proton exchange membrane material of a methanol fuel cell, which comprises the following steps:
1) 12mg of pale yellow transparent crystals prepared in example 3 of the present invention were weighed, added to 2-3mL of isopropanol solution, and dispersed in ultrasound for 30min.
2) 1500mg of Nafion aqueous solution (10%) was weighed into 3mL of isopropanol and stirred well.
3) Dropwise adding 1) to 2), and stirring for 4h.
4) Pouring the uniformly stirred liquid into a polytetrafluoroethylene mould, airing at room temperature, and carrying out post-treatment, namely taking the composite membrane.
Example 6
The invention discloses a preparation method of a proton exchange membrane material of a methanol fuel cell, which comprises the following steps:
1) 12mg of pale yellow transparent crystals prepared in example 3 of the present invention were weighed, added to 2-3mL of isopropanol solution, and dispersed in ultrasound for 30min.
2) 1500mg of Nafion aqueous solution (10%) was weighed into 3mL of isopropanol and stirred well.
3) Dropwise adding 1) to 2), and stirring for 6h.
4) Pouring the uniformly stirred liquid into a polytetrafluoroethylene mould, airing at room temperature, and carrying out post-treatment, namely taking the composite membrane.
Example 7
The invention discloses a preparation method of a proton exchange membrane material of a methanol fuel cell, which comprises the following steps:
1) 12mg of pale yellow transparent crystals prepared in example 3 of the present invention were weighed, added to 2-3mL of isopropanol solution, and dispersed in ultrasound for 30min.
2) 1500mg of Nafion aqueous solution (10%) was weighed into 3mL of isopropanol and stirred well.
3) Dropwise adding 1) to 2), and stirring for 8 hours.
4) Pouring the uniformly stirred liquid into a polytetrafluoroethylene mould, airing at room temperature, and carrying out post-treatment, namely taking the composite membrane.
In the above examples, the composite film prepared in example 7 was subjected to electrochemical testing using example 7 as the best example.
As shown in FIG. 8, it was found by electrochemical test that the proton conductivity of the composite membrane can reach 2.4X10 at 100deg.C and 98% RH -3 S·cm -1 。
As shown in FIG. 9, it was found by subjecting the composite membrane to a methanol fuel cell and testing that the composite membrane material had a weight of 72mW/cm 2 Is 1.4 times that of Nafion, and has a maximum current density of 432.6mA/cm 2 The ratio is improved by 1.3 times compared with Nafion. Therefore, the method has good application prospect in the methanol fuel cell.
In conclusion, the composite membrane material prepared by the invention has better proton conductivity under the conditions of high temperature and high humidity, and has the advantages of high temperature and high humidity of 98 percent,at 100 deg.C, its proton conductivity can be up to 2.4X10 -3 S·cm -1 . Secondly, the methanol fuel cell performance of the composite membrane is also very remarkable, with 72mW/cm 2 Is 1.4 times that of Nafion, and has a maximum current density of 432.6mA/cm 2 The ratio is improved by 1.3 times compared with Nafion.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: modifications and equivalents may be made to the specific embodiments of the invention without departing from the spirit and scope of the invention, which is intended to be covered by the claims.
Claims (5)
1. The organic framework material based on the five-fold interpenetrating hydrogen bonds is characterized by comprising the following chemical formula: { (TSM) & 2 (DBPy) & 2 (H) 2 O) n, where n is a positive integer, TSM is a tetra (4-sulfophenyl) methane anion of the formula { TSM } 4- DBPy is 1,1 '-diamino-4, 4' -bipyridine cation with a chemical formula of { C 10 H 12 N 4 } 2+ ；
DBPy 2+ Amino group on TSM 4- The sulfonic group and the free water molecules interact to form a 3D honeycomb-shaped framework, and five identical honeycomb-shaped framework structures are mutually penetrated to form a hydrogen bond organic framework with five penetration points;
three unique channels are arranged in the 3D honeycomb type framework and are named as C1, C2 and C3 respectively;
c1 is a quadrilateral channel, covered by a first type of TSM 4- Ligand occupation; c2 is a cross-shaped channel, covered by a second type of TSM 4- Ligand occupation; c3 is a rectangular channel, DBpy 2+ Ligand occupation;
TSM of the first type 4- The ligand is composed of a TSM 4- Sulfonic acid group and three 1/2 DBpy 2+ Is formed by hydrogen bonding;
TSM of the second type 4- The ligand is composed of a TSM 4- Sulfonic acid group and two 1/2 DBpy 2+ Is formed by hydrogen bonding;
the structural unit of the organic framework material based on the quintuple interpenetrating hydrogen bond belongs to a tetragonal system;
the space group of the organic framework material based on the five-fold interpenetrating hydrogen bonds is I-4, and the molecular formula is C 45 H 44 N 8 O 14 S 4 Unit cell parameters: α＝90.00°，β＝90.00°，γ＝90.00°，/>
the organic framework material based on the five-fold interpenetrating hydrogen bonds is formed by polymerizing a plurality of repeating units, and each repeating unit comprises a TSM 4- Two DBPy 2+ Two water molecules;
the proton conductivity of the organic framework material based on the five-fold interpenetrating hydrogen bonds is 1.21 multiplied by 10 at 98 percent of humidity and 100 DEG C -2 S·cm -1 ，E a ＝0.855eV。
2. The organic framework material based on the five-fold interpenetrating hydrogen bonds, according to claim 1, is a porous material, and has a temperature of 280 ℃ in a heat stabilization way.
3. The method for preparing the organic framework material based on the quintuple interpenetrating hydrogen bonds as claimed in claim 1 or 2, which is characterized by comprising the following steps:
1) Preparation of H 4 TSM ligand powder, H 4 The TSM ligand powder is completely dissolved in methanol to give H 4 TSM solution;completely dissolving DBpy.2I ligand in water to obtain DBPy.2I solution;
wherein H is 4 The molar ratio of TSM ligand to DBPy.2I ligand is (1-2): (2-5), wherein the molar ratio of the methanol to the water is (1-2), namely (1-2);
2) Mixing the two solutions at room temperature, and standing to obtain pale yellow transparent crystals, thus obtaining the organic frame material based on the five-fold interpenetrating hydrogen bonds.
4. The process according to claim 3, wherein H 4 The preparation process of the TSM ligand powder comprises the following steps: at N 2 Adding tetraphenyl methane into dichloromethane under the atmosphere, dropwise adding chlorosulfonic acid under ice bath, filtering after reaction, washing with dichloromethane, filtering, recrystallizing with methanol to obtain H 4 TSM ligand powder.
5. Use of the quintuple interpenetrating hydrogen bond based organic framework material according to claim 1 or 2 as proton conducting material.
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