CN115058019B - Three-dimensional metal sodium coordination polymer and preparation method and application thereof - Google Patents
Three-dimensional metal sodium coordination polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of complex preparation, and discloses a three-dimensional metal sodium coordination polymer, which has the chemical formula: [ Na ] 5 (TPE–PO 3 H 2 )(DMSO)(H 2 O) 2 ]· n Wherein n is a positive integer, TPE-PO 3 H 2 Is 4- (1, 2-tri (4-phosphonophenyl) vinyl) phenyl) phosphonic acid and DMSO is dimethyl sulfoxide. The structural unit belongs to a triclinic system, and the space group is P ‑ 1, molecular formula C 28 H 23 Na 5 O 23 P 4 S 1 . Each repeating unit comprises two water molecules, one DMSO molecule, five Na atoms and one TPE-PO 3 H 2 A molecule. In the three-dimensional metal sodium coordination polymer, na and an organic ligand TPE-PO 3 H 2 A minimum metal cluster is formed, and a one-dimensional metal cluster chain is formed through the connection between Na and Na. Solves the problem of low conductivity of the material under the medium and low temperature condition.
Description
Technical Field
The invention belongs to the technical field of complex preparation, and particularly relates to a three-dimensional metal sodium coordination polymer, and a preparation method and application thereof.
Background
In recent years, solid proton-conducting materials have been attracting attention due to their wide application in the fields of sensors, batteries, fuel cells, and the like. With environmental pollution, development of new renewable energy sources is urgent. In recent years, a range of crystalline materials such as Metal Organic Frameworks (MOFs), covalent Organic Frameworks (COFs), and hydrogen bond organic frameworks (HOFs) have received widespread attention as promising conductors and have rapidly progressed. The crystal not only has a designable and adjustable structure and performance, but also has high crystallinity, and provides a good material basis for in-depth research of proton conduction mechanism. MOFs having proton conductivity have proven to be useful for new energy fuel cells over the past few decades. Therefore, development of novel, inexpensive, high-performance proton-conducting materials has become a research hotspot.
Since MOFs have a high degree of crystallinity, single crystal X-ray diffraction can be used to determine their structure, which helps to explore the conduction mechanism. In addition, MOFs are easy to prepare and can be formed into composites with other materials to improve their chemical stability and proton conductivity. The metal ions and pores of MOFs can change the pH value or the hydrophilicity of the material through modification, so that the aim of influencing proton conduction is fulfilled. The chemical bonds between MOFs determine that the material is less stable than other materials and can therefore be recombined, making it a potentially a completely new generation of proton conducting materials. The current research shows that MOFs only show higher proton conductivity at high temperature, while MOFs synthesized by us have rich metal clusters, which can lead to high conductivity at medium and low temperature.
Disclosure of Invention
The invention aims to provide a three-dimensional metal sodium coordination polymer, a preparation method and application thereof, and solves the problem of low conductivity of the material.
The invention is realized by the following technical scheme:
a three-dimensional sodium metal coordination polymer having the formula: [ Na ] 5 (TPE–PO 3 H 2 )(DMSO)(H 2 O) 2 ]· n Wherein n is a positive integer, TPE-PO 3 H 2 Is 4- (1, 2-tri (4-phosphonophenyl) vinyl) phenyl) phosphonic acid and DMSO is dimethyl sulfoxide.
Further, the structural unit of the three-dimensional metal sodium coordination polymer belongs to a space group P-1, and the molecular formula is C 28 H 23 Na 5 O 23 P 4 S 1 Unit cell parameters:
α＝75.149(4)°,β＝79.977(4)°,γ＝83.394(5)°,/>
further, the three-dimensional metal sodium coordination polymer is formed by polymerizing a plurality of repeating units, wherein each repeating unit comprises two water molecules, one DMSO molecule, five Na atoms and one TPE-PO 3 H 2 A molecule.
Further, the thermal decomposition temperature of the three-dimensional sodium metal coordination polymer reaches 550 ℃.
Further, in the three-dimensional metal sodium coordination polymer, na and an organic ligand TPE-PO 3 H 2 A minimum metal cluster is formed, and a one-dimensional metal cluster chain is formed through the connection between Na and Na.
Further, the three-dimensional sodium metal coordination polymer has a maximum resistance value of 8Ω at 98% humidity and 60 ℃, and a conductivity of 1.13×10 -2 S cm -1 ，Ea＝0.60eV。
The invention also discloses a preparation method of the three-dimensional metal sodium coordination polymer, which comprises the following steps:
1) TPE-PO 3 H 2 The molar ratio of the catalyst to NaOH is 1: adding the mixture of water and DMSO in the ratio of (3-5) to obtain a reaction solution; wherein, the mol ratio of water to DMSO is 1 (1-2);
2) And (3) reacting the reaction solution at 90-120 ℃ for 48-96h, and standing for 24-48h at room temperature after the reaction is finished to obtain the three-dimensional metal sodium coordination polymer.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a three-dimensional metal sodium coordination polymer and a preparation method thereof, wherein the material passes through four TPE-PO 3 H 2 The ligand coordinates with five Na to form the minimum unit in the metal cluster, then through the connection of Na and Na,TPE-PO 3 H 2 the deprotonated phosphates on the ligands are interconnected, eventually forming one of the simplest metal clusters. The metal clusters are connected through Na to form a one-dimensional chain structure. The three-dimensional metal sodium coordination polymer prepared by the invention has higher purity through PXRD powder diffraction analysis data, thermal gravimetric analysis shows that the thermal stability is high, the decomposition temperature of a three-dimensional porous frame is 550 ℃, and the three-dimensional metal sodium coordination polymer has better performance on proton transportation, has better proton conductivity and can reach 1.13 multiplied by 10 -2 S cm -1 Is a novel proton conducting material.
Drawings
FIG. 1 is a schematic diagram of the coordination environment of the complex MOF-Na of the present invention;
FIG. 2 is a diagram of the smallest metal cluster unit of the complex MOF-Na of the present invention;
FIG. 3 is a schematic representation of the three-dimensional structure of the complex MOF-Na of the present invention;
FIG. 4 is a schematic diagram of the measured PXRD and simulated PXRD of the complex MOF-Na of the present invention;
FIG. 5 is a thermogravimetric analysis of the complex MOF-Na according to the present invention;
FIG. 6 is an impedance diagram of the complex MOF-Na of the present invention;
FIG. 7 is a graph showing the analysis of activation energy of the complex MOF-Na of the present invention.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
The invention discloses a three-dimensional metal sodium coordination polymer, which has the chemical formula: [ Na ] 5 (TPE–PO 3 H 2 )(DMSO)(H 2 O) 2 ]· n Wherein n is a positive integer, TPE-PO 3 H 2 Is 4- (1, 2-tri (4-phosphonophenyl) vinyl) phenyl) phosphonic acid and DMSO is dimethyl sulfoxide.
The invention also discloses a preparation method of the three-dimensional metal sodium coordination polymer, which comprises the following steps:
1) TPE-PO 3 H 2 Massage with NaOHThe molar ratio is 1: 3-5, adding the mixture into a mixed solution of water and DMSO to obtain a reaction solution; wherein, the mol ratio of water to DMSO is 1:1-2;
2) And (3) reacting the reaction solution at 100 ℃ for 48-96 hours, and standing for 24-48 hours at room temperature after the reaction is finished to obtain the three-dimensional metal sodium coordination polymer.
The invention is described in further detail below with reference to examples:
example 1
A preparation method of a three-dimensional metal sodium coordination polymer, which comprises the following steps:
1) TPE-PO 3 H 2 The molar ratio of the catalyst to NaOH is 1:3 is added into 1mL of mixed solution of water and DMSO to obtain reaction solution; wherein, the mol ratio of water to DMSO is 1:1;
2) The reaction solution was transferred to a hydrothermal reaction vessel for solvothermal reaction at 100℃for 48 hours. And after the reaction is finished, standing for 24 hours at room temperature to obtain the three-dimensional metal sodium coordination polymer.
This example gives a yield of 65% Na 5 (TPE–PO 3 H 2 )(DMSO)(H 2 O) 2 ]· n Coordination polymer materials give lower crystal yields.
Example 2
A preparation method of a three-dimensional metal sodium coordination polymer, which comprises the following steps:
1) TPE-PO 3 H 2 The molar ratio of the catalyst to NaOH is 1:4, adding the mixture into 1mL of mixed solution of water and DMSO to obtain a reaction solution; wherein, the mol ratio of water to DMSO is 1:2;
2) The reaction solution was transferred to a hydrothermal reaction vessel to perform solvothermal reaction, and reacted at 120℃for 72 hours. And after the reaction is finished, standing for 48 hours at room temperature to obtain the three-dimensional metal sodium coordination polymer.
This example gives a yield of 70% Na 5 (TPE–PO 3 H 2 )(DMSO)(H 2 O) 2 ]· n Coordination polymer materials, the resulting crystalline particles are smaller.
Example 3
A preparation method of a three-dimensional metal sodium coordination polymer, which comprises the following steps:
1) TPE-PO 3 H 2 The molar ratio of the catalyst to NaOH is 1:5, adding the mixture into 1mL of mixed solution of water and DMSO to obtain a reaction solution; wherein, the mol ratio of water to DMSO is 1:1;
2) The reaction solution was transferred to a hydrothermal reaction vessel for solvothermal reaction at 100℃for 48 hours. And after the reaction is finished, standing for 48 hours at room temperature to obtain the three-dimensional metal sodium coordination polymer.
This example gives a yield of 80% Na 5 (TPE–PO 3 H 2 )(DMSO)(H 2 O) 2 ]· n Coordination polymer materials, the obtained crystal particles are larger and the yield is higher.
Example 4
A preparation method of a three-dimensional metal sodium coordination polymer, which comprises the following steps:
1) TPE-PO 3 H 2 The molar ratio of the catalyst to NaOH is 1:5, adding the mixture into 1mL of mixed solution of water and DMSO to obtain a reaction solution; wherein, the mol ratio of water to DMSO is 1:2;
2) The reaction solution is transferred into a hydrothermal reaction kettle to carry out solvothermal reaction, and the reaction is carried out for 96 hours at 90 ℃. And after the reaction is finished, standing for 48 hours at room temperature to obtain the three-dimensional metal sodium coordination polymer.
This example gives a yield of [ Na ] of 76% 5 (TPE–PO 3 H 2 )(DMSO)(H 2 O) 2 ]· n Coordination polymer materials give higher crystal yields but smaller particles.
In the above examples, the three-dimensional metal sodium coordination polymer prepared in example 3 was monochromatized with a graphite monochromator on a Bruke smart APEXII CCD diffractometer with the best example of example 3
Ray, scan in omega-theta mode, collect diffraction point at 298K, correct structural analysis by full matrix least squares on F2 and use SHELXL =2014 software package is completed. The material is in a triclinic system, and the space group is P - 1, molecular formula C 28 H 23 Na 5 O 23 P 4 S 1 Unit cell parameters: />
α＝75.149(4)°,β＝79.977(4)°,γ＝83.394(5)°,/>
As shown in fig. 1-3, the structure of the material is formed by polymerizing a plurality of repeating units, and the material has the remarkable structural characteristics that: each repeating unit comprises two water molecules, one DMSO molecule, five Na atoms and one TPE-PO 3 H 2 A molecule. And Na with the organic ligand TPE-PO 3 H 2 A minimum metal cluster is formed, and a one-dimensional metal cluster chain is formed through the connection between Na and Na.
Through four TPE-PO 3 H 2 The ligand coordinates with five Na to form the minimum unit in the metal cluster, and then the TPE-PO is connected by Na2 and Na2 3 H 2 The deprotonated phosphates on the ligands are interconnected, eventually forming one of the simplest metal clusters. The metal clusters are connected through Na5 to form a one-dimensional chain structure.
As shown in FIG. 4, the obtained three-dimensional sodium metal coordination polymer powder sample and the powder diffraction data obtained by single crystals are compared, and the diffraction peak of the obtained three-dimensional sodium metal coordination polymer is consistent with the peak simulated by the X-single crystal diffraction data, 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. 5, the thermal stability of the three-dimensional sodium metal coordination polymer was obtained by thermogravimetric analysis. The three-dimensional structure of the obtained three-dimensional metal sodium coordination polymer can be stabilized to 550 ℃ through thermogravimetric analysis curve, and collapse occurs after that. The prepared material is a new material with practical application value.
As shown in FIG. 6, the three-dimensional metal sodium coordination polymer of the present invention has an impedance maximum impedance value of 8 at 60℃at 98% humidity. From the relation between impedance and conductivity, the conductivity of the material reaches 1.13×10 -2 Scm -1 。
As shown in fig. 7, the activation energy curve can be found to be ea=0.60 eV, conforming to the vehicle mechanism.
In conclusion, the three-dimensional metal sodium coordination polymer synthesized by the invention has one-dimensional chain, and the material has better proton conductivity under the condition of medium temperature and high humidity, and the proton conductivity can reach 1.13 multiplied by 10 at the temperature of 60 ℃ under the humidity of 98% -2 S cm -1 。
Claims (7)
1. The three-dimensional metal sodium coordination polymer is characterized by having a chemical formula: [ Na ] 5 (TPE–PO 3 H 2 ) (DMSO) (H 2 O) 2 ]· n Wherein n is a positive integer, TPE-PO 3 H 2 4- (1, 2-tris (4-phosphonophenyl) vinyl) phenyl) phosphonic acid, DMSO dimethyl sulfoxide;
the structural unit of the three-dimensional metal sodium coordination polymer belongs to a triclinic system, and the space group isP − 1Molecular formula C 28 H 23 Na 5 O 23 P 4 S 1 Unit cell parameters: a= 9.3246 (7) a, b= 14.6353 (11) a, c= 16.3397 (11) aα=75.149(4)°,β=79.977(4)°,γ=83.394(5)°,V = 2116.7(3) Å 3 。
2. The three-dimensional sodium metal coordination polymer of claim 1, wherein the three-dimensional sodium metal coordination polymer is polymerized from a plurality of repeating units, each repeating unit comprising two water molecules, one DMSO molecule, five Na atoms, and one TPE-PO 3 H 2 A molecule.
3. The three-dimensional metal sodium coordination polymer according to claim 1, wherein the thermal decomposition temperature of the three-dimensional metal sodium coordination polymer is up to 550 ℃.
4. The three-dimensional metal sodium coordination polymer according to claim 1, wherein Na and an organic ligand TPE-PO are contained in the three-dimensional metal sodium coordination polymer 3 H 2 A minimum metal cluster is formed, and a one-dimensional metal cluster chain is formed through the connection between Na and Na.
5. The three-dimensional metal sodium coordination polymer according to claim 1, wherein the three-dimensional metal sodium coordination polymer has a maximum resistance value of 8Ω at 98% humidity and 60 ℃ and a conductivity of 1.13×10 −2 S cm −1 ，Ea=0.60eV。
6. The method for preparing the three-dimensional metal sodium coordination polymer according to any one of claims 1 to 5, which is characterized by comprising the following steps:
1) TPE-PO 3 H 2 The molar ratio of the catalyst to NaOH is 1: adding the mixture of water and DMSO in the ratio of (3-5) to obtain a reaction solution; wherein, the mol ratio of water to DMSO is 1 (1-2);
2) And (3) reacting the reaction solution at 90-120 ℃ for 48-96h, and standing for 24-48h at room temperature after the reaction is finished to obtain the three-dimensional metal sodium coordination polymer.
7. The use of the three-dimensional metallic sodium coordination polymer according to any one of claims 1 to 5 as a proton conductive material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106029674A (en) * | 2014-02-19 | 2016-10-12 | 加利福尼亚大学董事会 | Acid, solvent, and thermal resistant metal-organic frameworks |
| CN112048071A (en) * | 2020-07-31 | 2020-12-08 | 曲阜师范大学 | Preparation method and application of MOF material with adjustable proton conduction performance |
| ES2832528A1 (en) * | 2019-12-10 | 2021-06-10 | Fund Imdea Energia | METAL-ORGANIC NETWORKS BASED ON PYRENE-PHOSPHONATE (Machine-translation by Google Translate, not legally binding) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106029674A (en) * | 2014-02-19 | 2016-10-12 | 加利福尼亚大学董事会 | Acid, solvent, and thermal resistant metal-organic frameworks |
| ES2832528A1 (en) * | 2019-12-10 | 2021-06-10 | Fund Imdea Energia | METAL-ORGANIC NETWORKS BASED ON PYRENE-PHOSPHONATE (Machine-translation by Google Translate, not legally binding) |
| CN112048071A (en) * | 2020-07-31 | 2020-12-08 | 曲阜师范大学 | Preparation method and application of MOF material with adjustable proton conduction performance |
Non-Patent Citations (2)
| Title |
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| Chakraborty, Debabrata等."A Tetradentate Phosphonate Ligand-based Ni-MOF as a Support for Designing High-performance Proton-conducting Materials".《Chemistry - An Asian Journal》.2021,第16卷(第12期),第1861-4728页. * |
| Kim, Si Rim等."Enhancing Proton Conduction in a Metal-Organic Framework by Isomorphous Ligand Replacement".《Journal of the American Chemical Society 》.2013,第135卷(第3期),第963-966页. * |
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