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Preparation method of zirconium-based microporous coordination polymer

A coordination polymer and microporous technology, applied in chemical instruments and methods, compounds of group 4/14 elements of the periodic table, organic compounds of group 4/14 without C-metal bonds, etc., can solve the problem of small grain size Poor morphology, unfavorable large-scale production, low yield unfavorable large-scale production and other problems, to achieve the effect of complete morphology, improved solvent utilization, and uniform particle size

Active Publication Date: 2016-07-20
李亚丰
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In 2008, Cavka et al. [1] first reported the synthesis of UIO-66~68 (UIO=University of Oslo), the author will ZrCl 4 , UIO-66~68 was obtained by heating terephthalic acid or biphenyl dicarboxylic acid or terphenyl dicarboxylic acid and the solvent DMF at 140°C for 24 hours, among which UIO-66 has the problem of small grain size and poor morphology
[0006] The current synthetic methods are not conducive to large-scale production
For example, the use of inorganic acids as modifiers seriously reduces the quality of Zr-MOF, which is due to the node Zr 6 o 4 (OH) 4 In addition, the quality of Zr-MOF obtained by using organic monocarboxylic acid as a regulator is better, but the yield is too low to be conducive to large-scale production.

Method used

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  • Preparation method of zirconium-based microporous coordination polymer
  • Preparation method of zirconium-based microporous coordination polymer
  • Preparation method of zirconium-based microporous coordination polymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Example 1 A preparation method of a zirconium-based microporous coordination polymer, the steps and conditions are as follows: Step 1, under stirring at normal temperature and pressure, as a base material, 51.9g of ZrOCl was mixed in a 50L reaction kettle 2 ·8H 2 O (0.160mol) and 29.2g terephthalic acid (0.176mol) were added to a mixed solvent of 1.2L acetic acid (20.8mol) and 10L of N,N'-dimethylformamide (128mol) to prepare a mixed solution ; ZrOCl 2 ·8H 2 The molar ratio of O: terephthalic acid: acetic acid: N,N'-dimethylformamide is 1:1.1:130:800.

[0030] In step 2, the temperature of the mixed solution in step 1 is raised to 120°C. The total reaction time is 28 hours. The base material is first reacted for 4 hours, and then according to the same ratio as the base material, 51.9g of ZrOCl is added every 4 hours 2 ·8H 2 O (0.160mol) and 29.2g terephthalic acid (0.176mol) were added 5 times in total, and then reacted for 4 hours to stop the reaction. Zr-MOF was s...

Embodiment 2

[0032] Example 2 A preparation method of a zirconium-based microporous coordination polymer, the steps and conditions are as follows: Step 1, under normal temperature and pressure stirring, as a base material, in a 50L reaction kettle, 51.9gZrOCl 2 ·8H 2 O (0.160mol) and 29.2g terephthalic acid (0.176mol) were added to a mixed solvent of 0.6L acetic acid (10.4mol) and 5L of N,N'-dimethylformamide (64mol) to prepare a mixed solution ; ZrOCl 2 ·8H 2 The molar ratio of O: terephthalic acid: acetic acid: N,N'-dimethylformamide is 1:1.1:65:400.

[0033] Step 2, the temperature of the mixed solution in step 1 is raised to 120°C, the total reaction time is 27 hours, the bottom material is reacted for 3 hours first, and then the ZrOCl 2 ·8H 2 : The mol ratio of terephthalic acid is 1:0.45, and feed 103.8gZrOCl is added every 3 hours 2 ·8H 2 O (0.320mol) and 23.9g terephthalic acid (0.144mol) were added 6 times in total, and then reacted for 6 hours to stop the reaction. Zr-MOF w...

Embodiment 3

[0035] Example 3 A preparation method of a zirconium-based microporous coordination polymer, the steps and conditions are as follows: Step 1, under normal temperature and pressure stirring, as a base material, in a 50L reaction kettle, 37.3gZrCl 4 (0.160mol) and 24.3g2-aminoterephthalic acid (0.144mol) were added to a mixed solvent of 0.717L propionic acid (9.6mol) and 10L of N,N'-dimethylformamide (128mol) to obtain Mixed solution; ZrCl 4 : The molar ratio of terephthalic acid: acetic acid: N,N'-dimethylformamide is 1:0.9:60:800.

[0036] In step 2, the temperature of the mixed solution in step 1 is raised to 140°C, and the total reaction time is 30 hours. The base material is first reacted for 6 hours, and then according to the same ratio as the base material, 37.3g of ZrCl is added every 6 hours 4 (0.160mol) and 24.3g 2-aminoterephthalic acid (0.144mol), add a total of 3 times, react for another 6 hours to stop the reaction, separate by centrifugation or filtration, wash t...

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Abstract

The invention provides a preparation method of a zirconium-based microporous coordination polymer. The preparation method includes: utilizing organic monocarboxylic acid which is simple as a regulator. The organic monocarboxylic acid can promote forming of a Zr6O4(OH)4(CO2)12 cluster, so that influence of water contained on Zr6O4(OH)4 is avoided, forming of Zr-MOF is facilitated, and quality of Zr-MOF is guaranteed. ZrO2+salt containing crystal water, such as ZrOCl2.8H2O is selected as zirconium salt, so that cost can be lowered, water in a trace amount can be guided in to promote generation of the Zr6O4(OH)4(CO2)12 cluster. A periodic adding mode is adopted, so that generation of a reactant can be accelerated, technical process can be shortened effectively, solvent utilization rate is increased, and reaction efficiency is improved finally; more importantly, product quality is guaranteed. The zirconium-based microporous coordination polymer is uniform in grain size, high in crystallinity, complete in shape and suitable for gas storage and separation and serving as a carrier. By using the method, quality such as crystallinity, specific surface area and grain size uniformity of Zr-MOF can be guaranteed, and the zirconium-based microporous coordination polymer is suitable for large-scale production.

Description

technical field [0001] The invention relates to a preparation method of a zirconium-based microporous coordination polymer. Background technique [0002] Zirconium-based microporous coordination polymers (Zr-MOF) are composed of Zr 6 o 4 (OH) 4 (CO 2 ) 12 As a porous compound with a three-dimensional pore structure composed of nodes and organic ligands as linkers, the general structural formula after dehydration is described as ZrOL, where L is an organic ligand. Zirconium-based microporous coordination polymers have received extensive attention due to their large specific surface area, high crystallinity, uniform pore channels, high thermal stability, and good chemical stability to organic solvents, water, acid or alkali, and air. Due to these characteristics, zirconium-based microporous coordination polymers have broad application prospects in gas separation, storage, drug sustained release, environmental treatment, adsorption catalysis, and chemical sensing, and the ...

Claims

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Application Information

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IPC IPC(8): C07F7/00
CPCC07F7/003
Inventor 李亚丰
Owner 李亚丰
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