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Polyacid-based metal organic frame proton conductor material of acid molecule functionalization and preparation method thereof

A technology of organic framework and molecular function, applied in the field of polyacid-based metal-organic framework proton conductor materials and its preparation, can solve the problems of unstable crystal water, reduced electrical conductivity, and easy loss, so as to increase the effective concentration and improve the proton conduction performance, beneficial effect of proton conduction

Inactive Publication Date: 2017-07-21
XIJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Although heteropolyacids have high electrical conductivity, their crystal water is unstable and easy to lose, which leads to a rapid decrease in electrical conductivity, so there are still great obstacles in the actual application process.

Method used

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  • Polyacid-based metal organic frame proton conductor material of acid molecule functionalization and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] In this example, H 2 SO 4 Molecularly functionalized POM-MOF hybrid material, the specific structure is shown in formula (II):

[0024] h 2 SO 4 @[Ag 8 L 5 ] (PMo 12 o 40 )·(H 2 O) 10 (Ⅱ)

[0025] The synthesis steps are as follows:

[0026] 1) [Ag 8 L 5 ] (PMo 12 o 40 )·(H 2 O) 10 Synthesis:

[0027] H 3 PMo 12 o 40 12H 2 O (0.30 g, 0.15 mmol), AgNO 3 (0.17 g, 1.00 mmol), HL (0.03 g, 0.21 mmol) and H 2 O (10 mL) was prepared into a mixed solution, stirred at room temperature for one hour, and then washed with 1 M HNO 3 The pH was adjusted to the range of 1.60-2.00, and then the mixed solution was transferred to a 18 mL high-temperature and high-pressure reactor, and placed in an oven at 160 °C for three days. After the reaction, the reactor was slowly cooled to room temperature at a cooling rate of 10 °C / h, filtered, rinsed with distilled water, and dried at room temperature to obtain yellow blocky crystals with a yield of 52%.

[0028] 2) H ...

Embodiment 2

[0031] In this example, H 3 PO 4 Molecularly functionalized POM-MOF hybrid material, the specific structure is shown in formula (Ⅲ):

[0032] h 3 PO 4 @[Ag 8 L 5 ] (PMo 12 o 40 )·(H 2 O) 10 (Ⅲ)

[0033] The synthesis steps are as follows:

[0034] 1) [Ag 8 L 5 ] (PMo 12 o 40 )·(H 2 O) 10 Synthesis:

[0035] H 3 PMo 12 o 40 12H 2 O (0.30 g, 0.15 mmol) , AgNO 3 (0.17 g, 1.00 mmol), HL (0.03 g, 0.21 mmol) and H 2 O (10 mL) was prepared into a mixed solution, stirred at room temperature for one hour, and then washed with 1 M HNO 3 The pH was adjusted to the range of 1.60-2.00, and then the mixed solution was transferred to a 18 mL high-temperature and high-pressure reactor, and placed in an oven at 160 °C for three days. After the reaction, the reactor was slowly cooled to room temperature at a cooling rate of 10 °C / h, filtered, rinsed with distilled water, and dried at room temperature to obtain yellow blocky crystals with a yield of 52%.

[0036] 2) H ...

Embodiment 3

[0039] In this example, H 2 SO 4 Molecularly functionalized POM-MOF hybrid material, the specific structure is shown in formula (IV):

[0040] h 2 SO 4 @[Ag 8 L 5 ](PW 12 o 40 )·(H 2 O) 13 (IV)

[0041] The synthesis steps are as follows:

[0042] 1) [Ag 8 L 5 ](PW 12 o 40 )·(H 2 O) 13 Synthesis:

[0043] H 3 PW 12 o 40 12H 2 O (0.30 g, 0.097 mmol), AgNO 3 (0.17 g, 1.00 mmol), HL (0.03 g, 0.21 mmol) and H 2 O (10 mL) was prepared into a mixed solution, stirred at room temperature for one hour, and then washed with 1 M HNO 3 The pH was adjusted to the range of 1.60-2.00, and then the mixed solution was transferred to a 18 mL high-temperature and high-pressure reactor, and placed in an oven at 160 °C for three days. After the reaction, the reactor was slowly cooled to room temperature at a cooling rate of 10 °C / h, filtered, rinsed with distilled water, and dried at room temperature to obtain yellow blocky crystals with a yield of 58%.

[0044] 2) H 2 S...

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Abstract

The invention discloses a polyacid-based metal organic frame proton conductor material of inorganic acid molecule functionalization. Polyanions and crystal water molecules are domain-limited in pore canals of the metal organic frame, wherein the structure thereof is HAaPOM-MOF, wherein HA is one of H2SO4 or H3PO4; and POM-MOF is the polyacid-based metal organic frame, and is one of [Ag8L5](PMo12O40)(H2O)10 or [Ag8L5](PW12O40)(H2O)13, wherein L is 5-phenyl tetrazole. The invention further discloses a preparation method for the polyacid-based metal organic frame proton conductor material of the inorganic acid molecule functionalization. The preparation method comprises the following steps: firstly preparing the polyacid-based metal organic frame, uniformly mixing the prepared polyacid-based metal organic frame and HA solution, separating the material, washing, drying to obtain the polyacid-based metal organic frame proton conductor material of the inorganic acid molecule functionalization.

Description

technical field [0001] The invention belongs to the field of energy applications, and in particular relates to a polyacid-based metal-organic framework proton conductor material functionalized with acid molecules and a preparation method thereof. Background technique [0002] Solid electrolyte, also known as superionic conductor (or fast ion conductor), generally refers to a solid substance whose conductivity is greater than 10 at room temperature or slightly higher temperature. -2 S cm -1 , a substance with an activation energy less than 0.5 eV. Their electrical conductivity is excellent, between aqueous electrolytes and semiconductors. Heteropolyacids are a kind of polynuclear complexes containing oxygen bridges. In solid state, heteropolyacids are mainly composed of protons, heteropolyanions and water (structural water and crystal water). There are two types of protons in heteropolyacid crystals: one is the delocalized hydrated protons connected to the heteropolyanion...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G83/00
Inventor 朱敏任花萍李克轩丁思懿田少鹏马强张阳阳
Owner XIJING UNIV
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