CN112661971B - Thorium coordination polymer, preparation method thereof and application thereof in propyne storage - Google Patents
Thorium coordination polymer, preparation method thereof and application thereof in propyne storage Download PDFInfo
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- CN112661971B CN112661971B CN202011528741.9A CN202011528741A CN112661971B CN 112661971 B CN112661971 B CN 112661971B CN 202011528741 A CN202011528741 A CN 202011528741A CN 112661971 B CN112661971 B CN 112661971B
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Abstract
The invention provides a thorium coordination polymer, a preparation method thereof and application thereof in propyne storage. The chemical formula of the thorium coordination polymer is [ Th6O4(OH)4(C14H4F4O4)6(H2O)6]，C14H4F4O4Is a molecular formula of 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid without two carboxyl protons, belongs to a cubic crystal system, and has a space group ofFm‑ 3m(ii) a Unit cell parameter ofa=28 to 28.1 angstrom,b=28 to 28.1 angstrom,c=28 to 28.1 angstrom,
=90º，
=90º，
=90º，Zand = 4. The preparation method of the thorium coordination polymer comprises the following steps: mixing thorium salt, 3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid, nitric acid and a solvent, transferring the mixture into a reaction kettle, and reacting under the condition of 358-373K to obtain the thorium coordination polymer. The thorium coordination polymer can be used for storing propyne gas.
Description
Technical Field
The invention belongs to the field of coordination chemistry, and particularly relates to a thorium coordination polymer, a preparation method of the thorium coordination polymer and application of the thorium coordination polymer in propyne storage.
Background
Metal-Organic Framework (MOF), also known as porous coordination polymer, is a novel porous crystalline solid material formed by Organic ligands bridging inorganic Metal ions or Metal clusters through coordination bonds.
Many common substances, such as carbon materials and zeolite materials, are porous materials that have long been used as adsorbents. For better gas handling, there is an urgent need to develop porous materials with large storage capacity and high separation efficiency, especially those with high porosity and good modularity of different sizes. In this context, many new porous adsorbents, such as Metal Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs), and hydrogen bonded organic frameworks (HOFs), have been developed over the last two decades.
Among the different types of framework materials, porous coordination polymers are organic-inorganic hybrid solids formed by coordination of organic ligands to metal ions or metal clusters. Moderate bond strengths (90-350 kJ/mol, in contrast to 1-170 kJ/mol and 300-600 kJ/mol for HOFs and COFs, respectively) and a wide variety of porous structures give them high crystallinity, excellent porosity, high modularity, and diverse functionalities. Therefore, the compounds have important application values in various fields of gas adsorption, adsorption and separation, proton conduction, fluorescence sensing, drug delivery, heterogeneous catalytic materials and the like. Among them, in the aspect of gas adsorption, the porous material has super-large surface area, porous property and high crystallinity, and the interior of the pore channel has regularly and densely arranged adsorption active sites, so that the porous material has great superiority in the aspect of gas adsorption.
The rapid worldwide increase in the demand for fossil fuels has brought about significant environmental problems, particularly climate change due to carbon emissions. Gaseous fuels are more environmentally friendly due to their lower carbon emissions and higher energy density than liquid petroleum and solid coal. The main challenges of gaseous fuels are their transportation, storage and conversion, which are usually achieved under demanding conditions and consume large amounts of energy due to their very low boiling point, low density, high critical pressure and high diffusivity. Current gaseous fuel storage technologies include cryogenic liquefaction or high pressure compression at ambient temperature (typically hundreds of atmospheres), and thus are particularly demanding on the equipment. In order to achieve inexpensive, safe and portable storage and transportation, it is necessary to perform adsorption and storage of gas under mild conditions. Propyne is one of the components of petroleum cracking and is an important industrial gas. It is one of the components of MAPP gas (soldering gas), and is also used as an important raw material for the products of medicine synthesis, fine chemical engineering, essence and perfume, etc. As a basic chemical raw material, it is generally stored in a steel cylinder under high pressure, and the development of storage of propyne under mild conditions is a prerequisite for the widespread use of propyne.
Disclosure of Invention
The invention provides a thorium coordination polymer and a preparation method and application thereof for storing propyne.
The invention provides a thorium coordination polymer with a chemical formula of [ Th6O4(OH)4(C14H4F4O4)6(H2O)6]，（C14H4F4O4Is a molecular formula of 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid without two carboxyl protons), belongs to a cubic crystal system, and has a space group ofFm-3m(ii) a Unit cell parameter ofa=28 to 28.1 angstrom,b=28 to 28.1 angstrom,c=28 to 28.1 angstrom,
= 90º，
= 90º，
= 90º，Z = 4。
the preparation method of the thorium coordination polymer comprises the following steps: mixing thorium salt, 3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid, nitric acid and a solvent, transferring the mixture into a reaction kettle, and reacting at 358-373K to obtain the thorium coordination polymer.
Wherein, 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid is an organic ligand, and the chemical structural formula is as follows:
preferably, the molar ratio of the thorium salt, the 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid and the nitric acid is 1: 1: 85.
preferably, the solvent is a mixed solvent of an organic solvent and water. More preferably, the solvent is a mixed solvent of DMF and deionized water.
Preferably, the thorium salt is thorium nitrate.
Preferably, the mass fraction of the nitric acid is 68%.
Preferably, the reaction time is 6 hours.
The thorium coordination polymer can be used for storing propyne gas. The organic ligand 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid has conjugated benzene rings, oxygen atoms with strong coordination capacity and naked fluorine atoms, and can synthesize a porous coordination polymer with a novel structure and special functions; meanwhile, fluorine atoms on the benzene ring are distributed on the inner surface of the pore channel to serve as adsorption sites and proper holes, so that the purpose of adsorbing the propine gas is achieved.
The invention has the advantages that: the thorium coordination polymer is synthesized, the preparation method is simple, easy to operate, high in yield and good in repeatability, and meets the requirement of expanded production; the adsorption amount of the thorium coordination polymer on the propyne gas at 298K per gram is 8.16 millimoles, and the thorium coordination polymer has good performance on storing the propyne gas.
Drawings
FIG. 1 is a molecular structure diagram of a thorium coordination polymer of the invention.
FIG. 2 is a drawing showing propyne absorption of the thorium coordination polymer at 298K.
Detailed Description
Coordination Polymer [ Th ] of the present invention6O4(OH)4(C14H4F4O4)6(H2O)6]Prepared by solvothermal methodThe formula is as follows:
6C14H6O4F4+6Th(NO3)3+H2O→[Th6O4(OH)4(C14H4F4O4)6(H2O)6]+18HNO3
C14H6O4F4is the molecular formula of 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid, C14H4O4F4Is a molecular formula of 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid without two carboxyl protons.
The invention is further illustrated with reference to the following specific embodiments and the accompanying drawings.
Example 1:
0.03 mmol (9.36 mg) of tetrafluorobiphenyldicarboxylic acid, 0.03 mmol (15 mg) of thorium nitrate and 2.56 mmol (160. mu.L) of concentrated nitric acid were weighed out, added to a mixed solvent of 2 ml of DMF and 0.5 ml of water, and mixed well to obtain a colorless transparent solution; then transferring the mixture into a polytetrafluoroethylene-lined high-pressure kettle with the volume of 20 ml, and reacting for 6 hours at constant temperature of 358-373K to obtain colorless octahedral crystals, namely the thorium coordination polymer [ Th6O4(OH)4(C14H4F4O4)6(H2O)6]， （C14H4F4O4Is a molecular formula of 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid without two carboxyl protons).
The colorless crystals obtained in example 1 were tested. The single crystal X-ray diffractometer tests show that the colorless crystal is the target compound, namely the thorium site polymer. The crystal X-ray diffraction data were measured using an Agilent SuperNova single crystal diffractometer. Diffraction data were collected in an ω -scan fashion with a MoK α molybdenum target (λ =1.54178 angstroms). All non-hydrogen coordinates were obtained by the SHELXL2018 program using the direct method and the full matrix least squares method, the "crystallographic parameters" of the compound are shown in Table 1, and the structure is shown in FIG. 1.
TABLE 1 thorium coordination polymers [ Th6O4(OH)4(C14H4F4O4)6(H2O)6](ii) crystallographic parameter and structure analysis of (C)14H4F4O4Is a molecular formula of 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid without two carboxyl protons).
Note:R1＝∑||F o|-|F c||/∑|F o|，wR 2＝[∑w(F o 2-F c 2)2/∑w(F o 2)2]0.5。
the thorium coordination polymer in the above example is a colorless octahedral crystal, the thorium ions are bridged by oxygen atoms to form a hexagonal cluster of octahedrons, the hexagonal cluster is bridged by 12 carboxylic acid groups to form 12-linked secondary structural units, and each secondary structural unit is bridged with 12 ligands to form a three-dimensional structure. Thus, it is a three-dimensional porous coordination polymer.
Taking 100 mg of the thorium coordination polymer obtained in example 1, a propyne adsorption performance test was performed at a temperature of 298K using a microphone gas adsorber (ASAP2020 HD88), which showed excellent propyne adsorption performance, as shown in FIG. 2.
Claims (8)
1. A thorium coordination polymer characterized in that: has the chemical formula of [ Th6O4(OH)4(C14H4F4O4)6(H2O)6]，C14H4F4O4Is a molecular formula of 3,3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid without two carboxyl protons, belongs to a cubic crystal system, and has a space group ofFm-3m(ii) a Unit cell parameter ofa=28 to 28.1 angstrom,b= 28-28.1 angstrom,c=28 to 28.1 angstrom,
= 90º，
= 90º，
= 90º，Z = 4。
2. a process for the preparation of a thorium coordination polymer according to claim 1, comprising the steps of: mixing thorium salt, 3',5,5' -tetrafluorobiphenyl-4, 4' -dicarboxylic acid, nitric acid and a solvent, transferring the mixture into a reaction kettle, and reacting at 358-373K to obtain the thorium coordination polymer.
3. A process for the preparation of a thorium coordination polymer according to claim 2, characterized in that: the solvent is a mixed solvent of an organic solvent and water.
4. A process for the preparation of a thorium coordination polymer according to claim 2, characterized in that: the solvent is a mixed solvent of DMF and deionized water.
5. A process for the preparation of a thorium coordination polymer according to claim 2, characterized in that: the thorium salt is thorium nitrate.
6. A process for the preparation of a thorium coordination polymer according to claim 2, characterized in that: the mass fraction of the nitric acid is 68%.
7. A process for the preparation of a thorium coordination polymer according to claim 2, characterized in that: the reaction time was 6 hours.
8. Use of a thorium coordination polymer according to claim 1, characterised in that it is used for the storage of propyne gas.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944680A (en) * | 2016-05-17 | 2016-09-21 | 浙江大学 | Method using absorption to separate propylene and propyne |
| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN108484924A (en) * | 2018-03-28 | 2018-09-04 | 江西师范大学 | A kind of nickel coordination polymer and preparation method thereof of separation acetylene/ethylene mixed gas |
| CN109293467A (en) * | 2018-11-09 | 2019-02-01 | 浙江大学 | A kind of method of adsorbing separation propylene, propine, propane and allene |
| CN110698686A (en) * | 2019-10-25 | 2020-01-17 | 江西师范大学 | Terbium coordination polymer for separating propyne/propylene mixed gas and preparation method thereof |
| CN111072987A (en) * | 2019-12-19 | 2020-04-28 | 北京工业大学 | Two fluorinated metal organic framework materials, preparation and low-carbon hydrocarbon separation application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944680A (en) * | 2016-05-17 | 2016-09-21 | 浙江大学 | Method using absorption to separate propylene and propyne |
| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN108484924A (en) * | 2018-03-28 | 2018-09-04 | 江西师范大学 | A kind of nickel coordination polymer and preparation method thereof of separation acetylene/ethylene mixed gas |
| CN109293467A (en) * | 2018-11-09 | 2019-02-01 | 浙江大学 | A kind of method of adsorbing separation propylene, propine, propane and allene |
| CN110698686A (en) * | 2019-10-25 | 2020-01-17 | 江西师范大学 | Terbium coordination polymer for separating propyne/propylene mixed gas and preparation method thereof |
| CN111072987A (en) * | 2019-12-19 | 2020-04-28 | 北京工业大学 | Two fluorinated metal organic framework materials, preparation and low-carbon hydrocarbon separation application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 四氟联苯二甲酸配体构建的稀...骨架的合成、结构和性能研究;林兆廷;《中国优秀硕士论文全文数据库 工程科技I辑》;20201015(第10期) * |
| 金属有机框架材料分离低碳烃的研究进展;崔希利等;《化工学报》;20180330;第69卷(第6期);第2339-2352页 * |
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