CN108623816A - A kind of micropore zinc (II) coordination polymer crystal and the preparation method and application thereof - Google Patents
A kind of micropore zinc (II) coordination polymer crystal and the preparation method and application thereof Download PDFInfo
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- CN108623816A CN108623816A CN201810734170.0A CN201810734170A CN108623816A CN 108623816 A CN108623816 A CN 108623816A CN 201810734170 A CN201810734170 A CN 201810734170A CN 108623816 A CN108623816 A CN 108623816A
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Abstract
The invention discloses a kind of micropore zinc (II) coordination polymer crystals and the preparation method and application thereof, the coordination polymer crystal is by by zinc nitrate hexahydrate, 1,4 two (imidazole radicals) butane, terephthalic acid (TPA), sodium hydroxide and water mixing carried out hydro-thermal reaction after 3~5 days, it is obtained after cooling crystallization, washed drying, which is [Zn2(1,4‑bib)(tpa)2]n.Isosorbide-5-Nitrae bib represents Isosorbide-5-Nitrae two (imidazole radicals) butane, and tpa represents terephthalic acid (TPA) acid group.Wherein, which forms car wheel structure as secondary structure unit using typical tetracarboxylic double-core zinc, is connected with the bridging of terephthalic acid (TPA) by (imidazole radicals) butane of Isosorbide-5-Nitrae two, forms a three-dimensional porous skeleton structure.There is coordination polymer crystal of the present invention good thermal stability, the crystal to have good adsorptivity and fluorescence property etc., can be applied to the fields such as petrochemical industry, fine chemistry industry.
Description
Technical field
The invention belongs to crystalline material technical fields, and in particular to a kind of micropore zinc (II) with adsorptivity and fluorescence
Coordination polymer crystal and the preparation method and application thereof.
Background technology
Metal organic coordination polymer (MCPs) is also known as metal organic framework compound (MOFs), mainly by metal ion
The New Solid with a variety of dimensional structures that (or ion cluster) is formed by coordinate bond with the organic ligand with certain function
Hydridization crystalline material.Due to many excellent characteristics that its pore passage structure determines, such as fluorescence property, gas absorption performance, catalysis
Activity and ion exchangeable etc. have important application in fields such as petrochemical industry, fine chemistry industries.This kind of material is also known in molecule
Not, the assembling of host-guest functional material, drug insertion etc. show wide application prospect.So far, it is tied about with novelty
The research frontier for designing synthesis and exploitation and being still very active of structure and the porous material of different chemical compositions.
People put into design synthesis with great interest and enthusiasm and find this kind of porous material with novel structure
In.In recent years, people are often used organic bridge ligand containing N and the mixing of the ligand of aromatics containing carboxyl regulates and controls its structure.Bigeminy miaow
Azoles ligand is usually used in the design of multidimensional coordination polymer and constructs as a kind of bridge ligand.Wherein, two imidazole rings are connected
Carbon chain lengths influence the final structure of metal coordinating polymer material.Currently, the MCPs materials synthesized as ligand using two bisglyoxalines
In it is more with 1,2- bis- (methylimidazole) ethane, 1,3- bis- (methylimidazole) propane.In addition, due to terephthalic acid (TPA) (H2tpa)
Coordination mode is versatile and flexible, and coordination site is abundant, is also widely used for the synthesis of metal coordinating polymer material, but with Isosorbide-5-Nitrae-two
The metal organic coordination polymer that (imidazole radicals) butane and terephthalic acid (TPA) regulate and control as mixed ligand has not been reported.
Invention content
The purpose of the present invention is to provide a kind of micropore zinc (II) coordination polymer crystals.
It is still another object of the present invention to provide the preparation methods of above-mentioned micropore zinc (II) coordination polymer crystal.
Another object of the present invention is to provide above-mentioned micropore zinc (II) coordination polymer crystals in fluorescent material and gas
Application in terms of sorbing material.
The invention is realized in this way a kind of micropore zinc (II) coordination polymer crystal, the chemical table of the coordination polymer
It is up to formula：[Zn2(1,4-bib)(tpa)2]n；Wherein, n is the natural number (infinity) not including 0；1,4-bib is organic
Ligand 1,4- diimidazole base butane, structure is as shown in following formula 1：
H2Tpa is terephthalic acid (TPA), and structure is as shown in following formula 2：
The coordination polymer is using the car wheel structure that typical tetracarboxylic double-core zinc forms as secondary structure unit, by 1,
(imidazole radicals) butane of 4- bis- is connected with the bridging of terephthalic acid (TPA), forms a three-dimensional porous skeleton structure.
The coordination polymer crystal belongs to monoclinic system, space group P21/ c, cell parameter are The ゜ of ゜, β=115 of α=γ=90.00,
The present invention further discloses the preparation method of above-mentioned micropore zinc (II) coordination polymer crystal, this method include with
Lower step：
Zinc nitrate hexahydrate, Isosorbide-5-Nitrae-two (imidazole radicals) butane, terephthalic acid (TPA), sodium hydroxide and water mixing, mixture is 110
Hydro-thermal reaction is carried out at~150 DEG C 3~5 days；Wherein, described by zinc nitrate hexahydrate, Isosorbide-5-Nitrae-two (imidazole radicals) butane, terephthaldehyde
The molar ratio of acid, sodium hydroxide and water is (0.1~1)：(0.05~0.5)：(0.1~1)：(0.05~0.5)：(110~
440)；
(2) by reaction product natural cooling crystallization, micropore zinc (II) coordination polymer crystalline substance is obtained after the washed drying of crystal
Body.
Preferably, in step (1), the mixture, which is placed in, to be sealed in autoclave with 5~10 DEG C per hour
Heating rate is warming up to 110~150 DEG C.
Preferably, in step (1), the hydro-thermal reaction time is 3~4 days.
The present invention further discloses above-mentioned micropore zinc (II) coordination polymer crystals in fluorescent material and gas-adsorbing material
Application in terms of material.
Compared with the prior art the shortcomings that and deficiency, the invention has the advantages that：
(1) coordination polymer of the present invention has good thermal stability, and it is 0.009231cm that largest hole, which is held,3/ g, average hole
Diameter isAs shown in fig. 6, when excitation wavelength is 314nm, micropore zinc (II) coordination polymer crystal is at 527nm wavelength
With strongest fluorescence emission peak.Illustrate that the microporous crystal has photoluminescent property.
(2) present invention can prepare micropore zinc (II) coordination polymer crystal, the preparation using one pot of hydro-thermal reaction
The advantages that method has process simple, easy to operate, yield height and good reproducibility.
Description of the drawings
Fig. 1 is the dissymmetrical structure unit of micropore zinc (II) coordination polymer prepared by the embodiment of the present invention；
Fig. 2 is micropore zinc (II) coordination polymer wheel shape secondary structure unit prepared by the embodiment of the present invention；
Fig. 3 is micropore zinc (II) coordination polymer three-dimensional pore space structure prepared by the embodiment of the present invention；
Fig. 4 is the powder x-ray diffraction figure of micropore zinc (II) coordination polymer prepared by the embodiment of the present invention；
Fig. 5 is micropore zinc (II) coordination polymer hot weight curve in a nitrogen atmosphere prepared by the embodiment of the present invention；
Fig. 6 is absorption figure of micropore zinc (II) coordination polymer to nitrogen of preparation of the embodiment of the present invention；
Fig. 7 is the fluorescence spectra of micropore zinc (II) coordination polymer prepared by the embodiment of the present invention.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Embodiment 1
Micropore zinc (II) coordination polymer crystal of the present embodiment belongs to monoclinic system, P21/ c space groups, cell parameter areThe ゜ of α=γ=90, β=115 °,
The concrete structure of zinc (II) coordination polymer crystal is as follows：
Contain 2 symmetrical Zn in the molecular structure dissymmetrical structure unit2+, 1 Isosorbide-5-Nitrae-two (imidazole radicals) butane ligand,
2 terephthalic acid (TPA) anion ligands.2 symmetrical Zn2+Coordination mode having the same, is all pentacoordinate configuration, center from
Sub- Zn2+Respectively with the nitrogen-atoms (N1), the 4 terephthalic acid (TPA) acid groups that come from 1 1,4- bis- (imidazole radicals) butane ligand
Carboxyl oxygen atom (O1, O2, O3 and O4) carries out monodentate ligand in ligand.In four above-mentioned terephthalic acid (TPA) anion ligands
Four carboxyls and two symmetrical Zn2+The car wheel structure of composition passes through Isosorbide-5-Nitrae-two (imidazole radicals) butane as secondary structure unit
It is connected with the bridging of terephthalic acid (TPA), forms a three-dimensional porous skeleton structure.
(1) by 0.1mmol zinc nitrate hexahydrates, 0.05mmol 1,4- bis- (imidazole radicals) butane, 0.1mmol terephthalic acid (TPA)s,
0.05mmol sodium hydroxides and the mixing of 277mmol water, stir 30min, said mixture are transferred to high pressure later at normal temperatures
In reaction kettle, hydro-thermal reaction is carried out at 150 DEG C 5 days；
(2) colourless rhomboidan is precipitated in reaction product natural cooling, rinses crystal with deionized water, is filtered under diminished pressure to obtain
White crystalline powder is placed in constant temperature in 110 DEG C of baking oven and obtains micropore zinc (II) coordination polymer 1 after 3 hours.
Embodiment 2
(1) by 0.15mmol zinc nitrate hexahydrates, 0.1mmol 1,4- bis- (imidazole radicals) butane, 0.2mmol terephthalic acid (TPA)s,
0.1mmol sodium hydroxides and the mixing of 229mmol water, stir 30min, it is anti-that said mixture is transferred to high pressure later at normal temperatures
It answers in kettle, hydro-thermal reaction is carried out at 120 DEG C 3 days；
(2) reaction product natural cooling is analysed into colourless bulk crystals, rinses crystal with deionized water, is filtered under diminished pressure to obtain white
Color crystal powder is placed in constant temperature in 110 DEG C of baking oven and obtains micropore zinc (II) coordination polymer 2 after 3 hours.
Embodiment 3
(1) by 0.2mmol zinc nitrate hexahydrates, 0.2mmol 1,4- bis- (imidazole radicals) butane, 0.15mmol terephthalic acid (TPA)s,
0.15mmol sodium hydroxides and the mixing of 300mmol water, stir 30min, said mixture are transferred to high pressure later at normal temperatures
Hydro-thermal reaction is carried out in reaction kettle, after being warming up to 120~150 DEG C with 5~10 DEG C per hour of heating rate 3~4 days；
(2) by reaction product natural cooling crystallization, crystal is rinsed with deionization, is filtered under diminished pressure to obtain white crystalline powder,
It is placed in constant temperature in 110 DEG C of baking oven and obtains sodium (I) coordination polymer 3 after 3 hours.
Effect example 1
The further characterization of micropore zinc (II) coordination polymer 3 is made in Example 3, and process is as follows：
(1) crystal structure determination of coordination polymer
The monocrystalline that suitable dimension is 0.25mm × 0.18mm × 0.15mm is chosen under the microscope carries out X-ray at room temperature
Diffraction experiment.Diffraction data is collected in Bruker-Apex П X-ray single crystal diffractometers, with the Mo-K of graphite monochromator monochromatization
Alpha rayPoint diffraction is collected with ω -2 θ scan modes.Total data through the factor and empirical absorption correction,
Crystal structure is solved using a program by direct method, and hydrogen atom synthesizes and be fixed on calculated optimum position by difference Fourier
It determines.With mono- programs of SHELX-97, to whole non-hydrogen atoms and its anisotropy thermal parameter carried out based on complete matrix most
Small square law amendment.Detailed axonometry data are shown in Table 1, and important bond distance and bond angle data are shown in 2, and crystal structure is shown in Fig. 1, figure
2 and Fig. 3.
The predominant crystal data of 1 zinc of table (II) coordination polymer 3
In table 1, R1=∑ (| | Fo|-|Fc||)/∑|Fo|, wR2=[∑ w (Fo 2-|Fc 2)2/∑w(Fo)2]1/2。
The important bond distance of 2 zinc of table (II) coordination polymer 3With bond angle (°)
(2) the phase purity characterization of coordination polymer
The powder X-ray RD characterization of coordination polymer shows it with reliable phase purity, for its as gas adsorption material with
Fluorescent material application provides guarantee, sees Fig. 4 (instrument models：Bruker/D8Advance).
(3) the thermal stability characterization of coordination polymer
The thermogravimetric analysis characterization of coordination polymer shows that its skeleton still keeps stable until 370 DEG C or so, has preferable
Thermal stability, for it, as application material, further exploitation provides thermal stability guarantee, sees Fig. 5 (instrument models：SDT
Q600)。
Effect example 2
Physical absorption is tested：The adsorption property that low temperature 77K can be used to illustrate poromerics from adsorption experiment.Weigh about 0.2g
Synthetic sample, placed it in vacuum drying chamber after grinding, allow it to lose adsorption within 6 hours in about 120 DEG C of heating in vacuum
Hydrone is subsequently transferred in physical adsorption appearance sample cell, and after 12 hours, accurately measure sample quality is 120 DEG C of automatic deaeratings
Above-mentioned sample cell is transferred to work station by 0.2136g, by measuring a series of nitrogen than pressure P/PoLower sample adsorption of nitrogen tolerance can
Nitrogen adsorption isothermal curve is drawn out, with the included software data processing of instrument, the largest hole appearance for recording sample is
0.009231cm3/ g, average pore size are
Fluorescence experiments：It is put in sepectrophotofluorometer sample cell after solid sample is ground film-making, by light source atmosphere arc lamp
The light sent out makes it become interrupted light by chopper, is used as fluorescent material after exciting light monochromator becomes monochromatic light after
Exciting light, when mapping fluorescence emission time spectrum, the grating of exciting light monochromator is fixed at a length of 314nm of excitation light wave,
Emission spectrum is recorded, it can be seen from figure 7 that fluorescence intensity is maximum at 527nm wavelength, this is the best transmitting of sample
Wavelength.When mapping fluorescent exciting time spectrum, the grating of emission monochromator is fixed at 527nm wavelength, excitation spectrum is recorded,
The maximum intensity of excitation spectrum is present in 314nm wavelength.The best launch wavelength and excitation wavelength of sample in this way can be very
Good is mapped, and further illustrating synthetic sample has photoluminescent property.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (5)
1. a kind of micropore zinc (II) coordination polymer crystal, which is characterized in that the chemical expression of the coordination polymer is：[Zn2
(1,4-bib)(tpa)2]n；Wherein, n is the natural number not including 0；Isosorbide-5-Nitrae-bib represents Isosorbide-5-Nitrae-two (imidazole radicals) butane,
Tpa represents terephthalic acid (TPA) acid group；
The car wheel structure that the coordination polymer is formed using typical tetracarboxylic double-core zinc passes through Isosorbide-5-Nitrae-two as secondary structure unit
(imidazole radicals) butane is connected with the bridging of terephthalic acid (TPA), forms a three-dimensional porous skeleton structure.
2. the preparation method of zinc (II) coordination polymer crystal described in claim 1, which is characterized in that this method includes following
Step：
(1) zinc nitrate hexahydrate, Isosorbide-5-Nitrae-two (imidazole radicals) butane, terephthalic acid (TPA), sodium hydroxide and water are mixed, mixture exists
Hydro-thermal reaction is carried out at 110~150 DEG C 3~5 days；Wherein, it is described by zinc nitrate hexahydrate, Isosorbide-5-Nitrae-two (imidazole radicals) butane, to benzene
The molar ratio of dioctyl phthalate, sodium hydroxide and water is (0.1~1)：(0.05~0.5)：(0.1~1)：(0.05~0.5)：(110~
440)；
(2) by reaction product natural cooling crystallization, zinc (II) coordination polymer crystal is obtained after the washed drying of crystal.
3. the preparation method of zinc (II) coordination polymer as claimed in claim 2, which is characterized in that described in step (1)
Mixture is placed in be sealed in autoclave is warming up to 110~150 DEG C with 5~10 DEG C per hour of heating rate.
4. the preparation method of zinc (II) coordination polymer crystal as claimed in claim 3, which is characterized in that in step (1),
The hydro-thermal reaction time is 3~5 days.
5. zinc (II) coordination polymer crystal described in right 1 is in the application of absorption property and fluorescence property.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467712A (en) * | 2018-11-06 | 2019-03-15 | 安徽大学 | A kind of metal organic framework MOF-Zn fluorescent sensor material and its preparation method and application |
| CN110330515A (en) * | 2019-07-31 | 2019-10-15 | 商丘师范学院 | A kind of nitrogen oxygen mixed ligand Zn complex and preparation method thereof |
| CN112827471A (en) * | 2020-12-29 | 2021-05-25 | 南京凯创微锌环境技术有限公司 | Preparation method of deodorant for sheep farm |
| CN113603897A (en) * | 2021-08-25 | 2021-11-05 | 北京工业大学 | Preparation of zinc-based metal organic framework material and selective adsorption application thereof |
| CN116444806A (en) * | 2023-02-24 | 2023-07-18 | 福州大学 | Nickel-sulfur coordination polymer and preparation and application thereof |
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| CN105237551A (en) * | 2015-10-09 | 2016-01-13 | 北京师范大学 | Zinc-based metal organic framework materials having room temperature phosphorescence characteristic and preparation method thereof |
| CN105524091A (en) * | 2016-01-05 | 2016-04-27 | 天津师范大学 | 1, 4-dimethyl-2, 5-dimethylene bistriazole zinc complex single crystal and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237551A (en) * | 2015-10-09 | 2016-01-13 | 北京师范大学 | Zinc-based metal organic framework materials having room temperature phosphorescence characteristic and preparation method thereof |
| CN105524091A (en) * | 2016-01-05 | 2016-04-27 | 天津师范大学 | 1, 4-dimethyl-2, 5-dimethylene bistriazole zinc complex single crystal and application thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467712A (en) * | 2018-11-06 | 2019-03-15 | 安徽大学 | A kind of metal organic framework MOF-Zn fluorescent sensor material and its preparation method and application |
| CN110330515A (en) * | 2019-07-31 | 2019-10-15 | 商丘师范学院 | A kind of nitrogen oxygen mixed ligand Zn complex and preparation method thereof |
| CN110330515B (en) * | 2019-07-31 | 2021-06-25 | 商丘师范学院 | Nitrogen-oxygen mixed ligand zinc complex and preparation method thereof |
| CN112827471A (en) * | 2020-12-29 | 2021-05-25 | 南京凯创微锌环境技术有限公司 | Preparation method of deodorant for sheep farm |
| CN112827471B (en) * | 2020-12-29 | 2023-10-31 | 南京凯创微锌环境技术有限公司 | Preparation method of deodorant for sheep farm |
| CN113603897A (en) * | 2021-08-25 | 2021-11-05 | 北京工业大学 | Preparation of zinc-based metal organic framework material and selective adsorption application thereof |
| CN113603897B (en) * | 2021-08-25 | 2022-06-07 | 北京工业大学 | Preparation of zinc-based metal organic framework material and selective adsorption application thereof |
| CN116444806A (en) * | 2023-02-24 | 2023-07-18 | 福州大学 | Nickel-sulfur coordination polymer and preparation and application thereof |
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Application publication date: 20181009 |