Metal coordination polymer and preparation method and application thereof

A metal coordination and polymer technology, applied in the direction of copper organic compounds, nickel organic compounds, etc., can solve the problems of low electrical conductivity and low seebeck coefficient, and achieve the effects of stable properties, excellent thermoelectric performance, and low thermal conductivity.

Active Publication Date: 2011-05-04
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these materials generally have problems such as low seebeck coefficient and low conductivity.

Method used

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  • Metal coordination polymer and preparation method and application thereof
  • Metal coordination polymer and preparation method and application thereof
  • Metal coordination polymer and preparation method and application thereof

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Experimental program
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Effect test

preparation example Construction

[0033] The method for preparing the metal coordination polymer based on ethylene tetrathiolate provided by the invention is to use 1,3,4,6-tetrathiadicyclopentene-2,5-dione as raw material, through alkali and Metal salts generate metal complexes, and then generate charge transfer complexes through ammonium salts or other metal ions, and oxidize them to obtain the final product. The synthesis route is as follows:

[0034]

[0035] The material prepared by the present invention can be tested for thermoelectric performance by the following method: testing the thermoelectric performance of the product. The sample is pressed into tablets to obtain a regular cuboid, which is measured with a four-electrode method, and the resistance at different temperatures is obtained by measuring with a low-temperature electrical and magnetic performance system. The sample was also pressed into tablets, and the seebeck coefficient was measured on the sample with the Seebeck Measurement System (...

Embodiment 1

[0036] Embodiment 1, the metal coordination polymer based on ethylene tetrathiolate shown in the preparation formula a

[0037]

[0038] (formula a)

[0039] Put 1,3,4,6-tetrathiadicyclopentene-2,5-dione (170mg) into a 50ml three-necked flask, add 20ml of nitrogen-protected methanol solution with a concentration of 12mg / mL sodium methoxide, room temperature Stir under nitrogen protection for 1 hour. Inject 15 ml of methanol solution of nickel chloride hexahydrate with a concentration of 13 mg / mL into the above solution, and stir at room temperature for half an hour. Add 20 mL of tetradecyltrimethylammonium bromide methanol solution with a concentration of 27 mg / mL, and stir at room temperature for half an hour. The solid was obtained by suction filtration and washed with methanol and water. Vacuum dry overnight. The obtained solid was dissolved in 10 mL of methanol at a concentration of 4 mg / mL, 20 mg of iodine was added, and oxidized at room temperature for 3 hours to ...

Embodiment 2

[0046] Embodiment 2, the metal coordination polymer based on ethylene tetrathiolate shown in synthetic formula b

[0047]

[0048] (formula b)

[0049] Put 1,3,4,6-tetrathiadicyclopentene-2,5-dione (261mg) into a 50ml three-necked flask, add 20ml of methanol solution of sodium methoxide with a concentration of 15mg / mL under nitrogen protection, Stir at room temperature for 1 hour under nitrogen protection. Inject 15 ml of a methanol solution of nickel chloride hexahydrate with a concentration of 20 mg / mL into the above solution, and stir at room temperature for 1 hour. The solid was obtained by suction filtration and washed with methanol and water. Vacuum dry overnight. The obtained solid was dissolved in 10 mL of methanol at a concentration of 6 mg / mL, and oxidized in air at room temperature for 13 days to obtain 200 mg of an ethylene tetrathiolate-based metal coordination polymer represented by formula b, with a yield of 78.0%.

[0050] Figure 4 It is the photoelect...

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Abstract

The invention discloses a metal coordination polymer and a preparation method and application of the metal coordination polymer. The polymer has a general structure formula shown by the formula I, and in the general structure formula of the formula I, R is a tetrabutyl ammonium ion, a tetradecyl trimethyl ammonium ion, Na or Ni, and M is Zn, Ni, Cu, Au, Pd or Pt. The preparation method comprises the following steps of: firstly, under an inert atmosphere, reacting sodium methylate with 1,3,4,6-tetra-sulfur co-cyclopentadiene-2,5-dione in an organic solvent; secondly, adding organic solution of nickel chloride hexahydrate to continue reacting, and after that, adding organic solution of an ammonium salt to continue reacting; and finally, drying the mixture, and oxidizing the mixture with iodine or air to obtain the product. For the polymer, the electric conductivity at 320K reaches 12.4S / cm, the seebeck coefficient can reach 170 muV / K, the heat conductivity is 0.3 W / m / k, and the thermoelectric merit figure ZT can reach 0.04. So, the metal coordination polymer is an excellent p-type organic thermoelectric conversion material.

Description

technical field [0001] The invention relates to an organic thermoelectric material, in particular to a metal coordination polymer and its preparation method and application. Background technique [0002] In 1834, French physicist J.C.A.Peltier discovered that thermoelectric materials can provide conversion between electrical energy and thermal energy; in 1923, Seebeck reported that temperature differences can generate electromotive force (Seebeck effect) without Moving mechanical parts, where electric potentials can generate temperature differences (Peltier effect), have received much attention. The thermoelectric effect itself is reversible, either from electrical energy to thermal energy or from thermal energy to electrical energy. Although the scientific community at that time attached great importance to the discoveries of Peltier and Seebeck, the discoveries were not quickly transformed into applications. This is because the thermoelectric conversion efficiency of met...

Claims

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Application Information

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IPC IPC(8): C07F15/04C07F1/08
Inventor 朱道本马维祝徐伟孙祎萌
Owner INST OF CHEM CHINESE ACAD OF SCI
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