CN109456492A - One kind containing the metal-organic framework materials and preparation method thereof of Cu (II) - Google Patents
One kind containing the metal-organic framework materials and preparation method thereof of Cu (II) Download PDFInfo
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- CN109456492A CN109456492A CN201811304684.9A CN201811304684A CN109456492A CN 109456492 A CN109456492 A CN 109456492A CN 201811304684 A CN201811304684 A CN 201811304684A CN 109456492 A CN109456492 A CN 109456492A
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Abstract
The invention belongs to the synthesis field of metal-organic framework materials, in particular to a kind of metal-organic framework materials and preparation method thereof for containing Cu (II).Described its molecular formula containing Cu (II) metal-organic framework materials is that its molecular formula is { [Cu (C10H8N2)(C2H3O3)2]·(C2H6O2)}n, wherein C10H8N2For 4,4 '-bipyridyls.Described Cu (II) the metal-organic framework materials crystal anorthic system, P-1 space group, cell parameter area=8.0214 (8),b=11.0562 (11),c=11.2503 (11),α=84.437 (4) °,β=77.592 (4) °,γ=69.037 (4) °,V=909.72 (16)3.Metal-organic framework materials preparation method of the present invention containing Cu (II) is simple, convenient, and favorable reproducibility, yield are high, and the fault in material being synthesized is few, and crystallinity is high, and stability is good.
Description
Technical field
The present invention relates to the synthesis fields of metal-organic framework materials, and in particular to the gold of one kind Cu containing transition metal (II)
Belong to the preparation and its structure feature of organic framework material.
Background technique
Metal organic framework (metal-organic frameworks, MOFs) is by metal ion or metal cluster unit
There is with organic ligand by one kind that coordination is self-assembly of the crystalline material of periodical multidimensional network structure.Nearest two
During the last ten years, the design synthesis of MOFs causes the huge concern of people, this is not only to have structured diversity because of it, can
Design and tailorability, and it is found in gas and stores and separate, and is catalyzed, sensor, drug delivery, proton
The fields such as conductor all have potential application prospect.
Varied for the organic ligand of constructing MOFs, their majorities are containing carboxyl or ligand containing N, and the structure of ligand
Type is also miscellaneous.4,4 '-bipyridyls are because its rigidity and dimensions length on molecular structure is suitable for, and because it is matched by force
Capability and bridge linking effect are synthesized with transition metal ions assembling by it and have obtained structure novel, the metal of unique properties has
Machine framework material has caused the broad interest of chemist.
Before present patent application work, still not about 4,4 '-bipyridyls, Glycolic acid and CuSO4·5H2O is in second two
Alcohol/water in the mixed solvent be self-assembly of MOFs in terms of patent document and scientific paper report.
Summary of the invention
The purpose of the present invention is to provide a kind of novel metal-organic framework materials and preparation method thereof containing Cu (II).
The technical problems to be solved by the invention are achieved by the following technical programs:
One kind containing the metal-organic framework materials of Cu (II), and molecular formula is { [Cu (C10H8N2)(C2H3O3)2]·(C2H6O2)}n ,
Crystal belongs to anorthic system, P-1 space group, and cell parameter isa=8.0214 (8),b=11.0562 (11),c=11.2503
(11),α=84.437 (4) °,β=77.592 (4) °,γ=69.037 (4) °,V=909.72 (16)3.Its structure is based on
The bridging of 4,4 '-bipyridyls is coordinated and the six one-dimensional chain structures formed with configuration of metal ion Cu (II), adjacent
Interchain is further built into two-dimentional supramolecular structure by intermolecular strong O-HO hydrogen bond action.
The preparation method of metal-organic framework materials of the one kind containing Cu (II): by 4,4 '-bipyridyls, Glycolic acid and copper sulphate
It is added in the mixed solution of ethylene glycol and distilled water, filters after being sufficiently stirred, then the filtrate is placed in autoclave,
Slow cooling obtains the crystal of the metal-organic framework materials containing Cu (II) after carrying out heating reaction under the conditions of solvent heat.
Further, the heating temperature is 110 ~ 140 DEG C.
Further, the heating reaction time is 72 ~ 96 hours.
Further, the cooling is down to room temperature for 2 DEG C/h ~ 5 DEG C/h.
Further, the volume ratio of the mixed solution ethylene glycol and distilled water is 1:2.
Further, the copper sulphate, 4,4'-Bipyridine and Glycolic acid molar ratio are 1:1:2.
The invention has the following beneficial effects:
Metal-organic framework materials of the synthesis containing Cu (II) under the conditions of solvent heat are easily prepared for the first time, stability is good by the present invention,
The fault in material being synthesized is few, and crystallinity is high, and preparation method is simple, convenient, favorable reproducibility, pollution-free, has potential
Environmental benefit.
Detailed description of the invention
Fig. 1 is the dissymmetrical structure unit figure of metal-organic framework materials of the present invention containing Cu (II).
Fig. 2 is the one-dimensional catenary structure of metal-organic framework materials of the present invention containing Cu (II).
Fig. 3 is the supramolecular structured composition of two dimension of metal-organic framework materials of the present invention containing Cu (II).
Specific embodiment
The present invention will now be described in detail with reference to examples, and the examples are only preferred embodiments of the present invention,
It is not limitation of the invention.
Embodiment 1:
0.1mmol copper sulphate, 0.1mmol 4,4 '-bipyridyl and 0.2mmol Glycolic acid are dissolved in 20mL ethyl alcohol/distilled water
( V:V=1:2) in, it is filtered after stirring at normal temperature 20min, filtrate is transferred to the stainless steel cauldron for making lining with polytetrafluoroethylene (PTFE)
In, it is put into baking oven after stainless steel cauldron is sealed, 96h is reacted at 130 DEG C, be down to room temperature later with 2 DEG C/h, obtain
To the metal-organic framework materials crystal containing Cu (II), yield is 43.6% (being based on Cu).
Then the metal-organic framework materials crystal by above-mentioned containing Cu (II) carries out structural characterization
Crystal X-ray diffraction data is measured using Bruker Smart Apex CCD single crystal diffractometer.Graphite is used at 223K
Monochromatization Mo K alpha ray (λ=0.071073nm) it is used as radiation source, collect diffraction data.Scanning mode is φ-ω scanning,
And Lp factor correction and empirical absorption correction are carried out, absorption correction uses SADABS program.Metallic atom is determined using direct method
And the position coordinates of non-hydrogen atom, whole non-hydrogen atom coordinates and its anisotropy thermal parameter carry out complete matrix least square method and repair
Just, hydrogen atom is determined by theoretical plus hydrogen, and carries out isotropism refine.Crystallographic parameter is shown in Table 1, and structure is shown in Fig. 1, Fig. 2, figure
3。
The predominant crystal data of metal-organic framework materials crystal of the preparation of table 1 containing Cu (II)
| Empirical formula | C16H20N2O8Cu |
| Formular weight | 431.88 |
| Crystal size / mm | 0.30×0.25×0.22 |
| Crystal system | Triclinic |
| Space group | P-1 |
| a / Å | 8.0214(8) |
| b / Å | 11.0562(11) |
| c/ Å | 11.2503(11) |
| α / (º) | 84.437(4) |
| β / (º) | 77.592(4) |
| γ / (º) | 69.037(4) |
| V / Å 3 | 909.72(16) |
| Z | 4 |
| D c / (g·cm-3) | 1.577 |
| λ / nm | 0.071073 |
| Temperature / K | 223.15 |
| θ range / (º) | 2.68~28.31 |
| Collected reflections | 32734 |
| Unique reflections | 4538 |
| Observed reflection | 4002 |
| R int | 0.0447 |
| F(000) | 446 |
| μ / mm-1 | 1.248 |
| R 1 | 0.0303 |
| wR 2 | 0.0755 |
From the point of view of crystal structure, which is a two-dimentional supermolecule layer structure.
Fig. 1 depicts structural unit figure, it can be seen from the figure that metal center Cu atom uses the octoploids structure of hexa-coordinate deformation,
Respectively with 2 N atoms on two 4,4'-Bipyridines, 2 hydroxyl O atoms and 2 carboxylate radical O atoms on two Glycolic acids
Effect.The one-dimensional chain structure that the adjacent Ni metal (II) of each 4,4'-Bipyridine ligand bridging is formed, as shown in Figure 2.
Adjacent chain is further built into two-dimentional supermolecule layer structure by intermolecular strong hydrogen bonding O-HO effect, dissociates
Glycol molecule be attached in two-dimensional layer assembling structure by O-HO hydrogen bond action, as shown in Figure 3.
Embodiment 2:
0.11mmol copper sulphate, 0.1mmol 4,4 '-bipyridyl and 0.2mmol Glycolic acid are dissolved in 20mL ethyl alcohol/distillation
Water (V:V=1:2) in, it is filtered after stirring at normal temperature 20min, filtrate is transferred to the stainless steel reaction for making lining with polytetrafluoroethylene (PTFE)
It in kettle, is put into baking oven after stainless steel cauldron is sealed, 72h is reacted at 120 DEG C, be down to room temperature later with 5 DEG C/h,
The Inorganic-Organic Hybrid Material crystal containing cobalt is obtained, yield is 39.1% (being based on Cu).
Embodiment 3:
0.1mmol copper sulphate, 0.11mmol 4,4 '-bipyridyl and 0.22mmol Glycolic acid are dissolved in 20mL ethyl alcohol/distillation
Water (V:V=1:3) in, it is filtered after stirring at normal temperature 20min, filtrate is transferred to the stainless steel reaction for making lining with polytetrafluoroethylene (PTFE)
It in kettle, is put into baking oven after stainless steel cauldron is sealed, 84h is reacted at 150 DEG C, be down to room temperature later with 5 DEG C/h,
The Inorganic-Organic Hybrid Material crystal containing cobalt is obtained, yield is 42.9% (being based on Cu).
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (5)
1. one kind is { [Cu (C containing its molecular formula of the metal-organic framework materials of Cu (II)10H8N2)(C2H3O3)2]·
(C2H6O2)}n, wherein C10H8N2For 4,4 '-bipyridyls；
It is characterized in that, the copper metal organic framework material crystal belongs to anorthic system, P-1 space group, cell parameter isa=8.0214 (8),b=11.0562 (11),c=11.2503 (11),α=84.437 (4) °,β=77.592 (4) °,γ
=69.037 (4) °,V=909.72 (16)3。
2. the preparation method of the metal-organic framework materials containing Cu (II) according to claim 1, comprising the following steps: by sulphur
Sour copper, 4,4'-Bipyridine and Glycolic acid are added in the mixed solution of ethylene glycol and distilled water, filter after stirring, then by filtrate
Transfer is placed in autoclave progress water (solvent) thermal response, it is cooling after reaction, be obtained by filtration it is described containing Cu (II)
The crystal of metal-organic framework materials.
3. the preparation method of the metal-organic framework materials containing Cu (II) according to claim 2, which is characterized in that copper sulphate
Molal quantity and the ratio between the molal quantity of 4,4 '-bipyridyls and Glycolic acid be 1: 1: 2.
4. the preparation method of the metal-organic framework materials containing Cu (II) according to claim 2, which is characterized in that the second
Ethyl alcohol and distilled water volume ratio are 1:2 in the mixed solution of pure and mild distilled water.
5. the preparation method of the metal-organic framework materials containing Cu (II) according to claim 2, which is characterized in that the water
The temperature of thermal response is 130 DEG C, and the time of solvent thermal reaction is 96h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113388859A (en) * | 2021-05-19 | 2021-09-14 | 东华理工大学 | Th-MOF loaded Cu-based single-site catalytic material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008020218A1 (en) * | 2006-08-17 | 2008-02-21 | The University Court Of The University Of St Andrews | Adsorption and release of nitric oxide in metal organic frameworks |
| CN102952163A (en) * | 2011-08-26 | 2013-03-06 | 中国科学院大连化学物理研究所 | Preparation and sensing application of mixed-ligand metal-organic framework materials |
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- 2018-11-05 CN CN201811304684.9A patent/CN109456492A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008020218A1 (en) * | 2006-08-17 | 2008-02-21 | The University Court Of The University Of St Andrews | Adsorption and release of nitric oxide in metal organic frameworks |
| CN102952163A (en) * | 2011-08-26 | 2013-03-06 | 中国科学院大连化学物理研究所 | Preparation and sensing application of mixed-ligand metal-organic framework materials |
Non-Patent Citations (2)
| Title |
|---|
| A. CASTIÑEIRAS，等: "Weak Antiferromagnetism in Carboxylato Copper(II) Complexes of Bipyridines", 《ZEITSCHRIFT FÜR ANORGANISCHE UND ALLGEMEINE CHEMIE》 * |
| 李小芳，等: "基于配体邻菲啰啉和肉桂酸构筑的铜配合物的合成、电化学性质及与DNA的相互作用", 《材料科学与工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113388859A (en) * | 2021-05-19 | 2021-09-14 | 东华理工大学 | Th-MOF loaded Cu-based single-site catalytic material and preparation method and application thereof |
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Application publication date: 20190312 |