CN102584901A - Microporous nickel coordinate polymer as well as preparation method and application thereof - Google Patents
Microporous nickel coordinate polymer as well as preparation method and application thereof Download PDFInfo
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- CN102584901A CN102584901A CN2012100066688A CN201210006668A CN102584901A CN 102584901 A CN102584901 A CN 102584901A CN 2012100066688 A CN2012100066688 A CN 2012100066688A CN 201210006668 A CN201210006668 A CN 201210006668A CN 102584901 A CN102584901 A CN 102584901A
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Abstract
The invention discloses a microporous nickel coordinate polymer as well as a preparation method and application thereof. The nickel coordinate polymer is a compound with the following chemical formula {[Ni(L)(PTA)](DMF)2.5}n, wherein L is 1,3,5-tris(p-imidazole phenyl) benzene, PTA is terephthalic acid and DMF is N,N-dimethyl formamide. The compound is prepared by adopting a solvothermal method, and the obtained crystal has higher purity. After free solvent molecule is removed, the microporous nickel coordinate polymer presents subtriangular irregular microporous channels in the a-axis direction of the crystal. The complex can adsorb hydrogen gas in a large amount, and hardly adsorbs nitrogen gas, so that the complex has excellent gas separation effect, can be used as a gas adsorption separating agent, and has potential application value in the field of material sciences.
Description
Technical field
The present invention relates to micropore metal-organic coordination polymer material; Particularly a kind of nickel ligand polymer and preparation method and application thereof; Described nickel ligand polymer is the polymkeric substance with gra three-dimensional net structure of micropore, has the function of selective adsorption separating hydrogen gas and nitrogen.
Background technology
In recent years, construct the very big interest that the coordination polymer material with novel pore passage structure has caused people through the coordination of metals ion and organic multi-functional part.Not only have novel exquisite topology network architecture, and mainly be because they can show character or function (Yaghi, O.M. such as special light, electricity, magnetic, catalysis and fractionation by adsorption because of them; O ' Keeffe, M.; Ockwig, N.W.; Chae, H.K.; Eddaoudi, M.; Kim, J.Nature 2003,423, and 705; Kitagawa, S.; Kitaura, R.; Noro, S.Angew.Chem.Int.Ed.2004,43,2334; Roberts, J.; Scheidt, K.A.; Nguyen, S.T.; Hupp, J.T.Chem.Soc.Rev., 2009,38,1450).Yet design and construct the duct material that this type have special construction and performance and have very big challenge, wherein the design of organic ligand and selection are particularly important.This is because the duct size of this type of polymer materials has strict restriction and requires it that good stability is arranged.Interspersed structure can be used for controlling the size in duct, and interspersed structure can also increase the stability of polymkeric substance.According to the formed duct of IPN size; Kinetics radius size in conjunction with all gases molecule; The kinetics radius gas littler than duct effective radius is passed through, the gas that kinetics radius is bigger than duct effective radius then be difficult to through, thereby effectively realize selective adsorption.Up to now, this type of bibliographical information of material with selective adsorption performance is also less relatively.(for example: Dybtsev, D.N.; Chun, H.; Yoon, S.H.; Kim, D.; Kim, K.J.Am.Chem.Soc.2004,126,32; Humphrey, S.M.; Chang, J.-S.; Jhung, S.H.; Yoon, J.W.; Wood, P.T.Angew.Chem.Int.Ed.2007,46,272; Li, J.R.; Kuppler, R.J.; Zhou, H.C.Chem.Soc.Rev., 2009,38,1477. etc.).Synthetic and the exploration of this type material; The organic multi-functional part that such ligand polymer is constructed in particularly rational design and expansion is to this research field; And then will produce very big influence, and be material science injection great vitality to exploitation high-performance novel material.
Summary of the invention
The object of the present invention is to provide a kind of micropore nickel ligand polymer and preparation and application thereof, this material is the polymkeric substance with gra three-dimensional net structure of microvoid structure, has the function of selective adsorption separating hydrogen gas and nitrogen.
The chemical formula of micropore nickel ligand polymer of the present invention is { [Ni (L) (PTA)] (DMF)
2.5}
n, wherein L is 1,3,5-three (p-imidazoles phenyl) benzene, and PTA is a terephthalic acid, DMF is N, dinethylformamide; Main infrared absorption peak is 3128cm
-1, 1666cm
-1, 1606cm
-1, 1575cm
-1, 1523cm
-1, 1385cm
-1, 1308cm
-1, 1065cm
-1, 964cm
-1, 819cm
-1, 753cm
-1, 662cm
-1
The decomposition temperature of micropore nickel ligand polymer coordination main body framework of the present invention is 348 ℃.
Micropore nickel ligand polymer crystal of the present invention belongs to oblique system, and spacer is P2
1/ n, unit cell parameters is:
α=γ=90 °, β=92.152 (5) °;
The structure of micropore nickel ligand polymer of the present invention is: ligand L and metallic nickel form 6
3Two-dimensional network, part PTA is with 6 then
3Network is connected to form the three-dimensional micropore structure; Be filled with the solvent DMF molecule in the duct, channel diameter is about
One-piece construction is double IPN gra topology network architecture.
The compound method of micropore nickel ligand polymer of the present invention may further comprise the steps:
With organic ligand L, PTA, nickelous nitrate and pyridine join N, in the dinethylformamide solvent; This DMF mixing solutions is obtained block red monocrystalline through solvent thermal reaction, then with DMF washing, drying.
The mol ratio of described L and PTA is 1: 2～1: 3.
The mol ratio of described L and nickelous nitrate is 1: 1～1: 2.5.
The solvent thermal condition of said thermal response is to react 5 days down at 115～125 ℃, slowly drops to room temperature.
Thermal analysis experiment of the present invention shows that the coordination skeleton of this ligand polymer has higher thermostability.Gas adsorption experiment shows that it can adsorb more a large amount of hydrogen, but similarity condition absorption nitrogen seldom down.Therefore, this ligand polymer can be used as the agent of potential gas delivery, has a good application prospect at material science.
Description of drawings
Fig. 1 { [Ni (L) (PTA)] (DMF)
2.5}
nThermogram;
Fig. 2 { [Ni (L) (PTA)] (DMF)
2.5}
nPowder diagram;
Fig. 3 { [Ni (L) (PTA)] (DMF)
2.5}
nMode of connection figure;
Fig. 4 { [Ni (L) (PTA)] (DMF)
2.5}
nThree-dimensional net structure figure;
Fig. 5 { [Ni (L) (PTA)] (DMF)
2.5}
nGas adsorption figure.
Embodiment
Synthesizing of embodiment 1A title complex:
Just organic ligand 1,3,5-three (p-imidazoles phenyl) benzene (0.1 mmole; 50.4 terephthalic acid (0.2 mmole, 33.2 milligrams) milligram); Nickelous nitrate hexahydrate (0.1 mmole; 29.1 milligram) be dissolved in 10 milliliters of N, in the dinethylformamide solvent, this DMF mixed the molten solvent thermal reaction still of packing into 2 of pyridines.Reacted 5 days down at 120 ℃, be cooled to room temperature naturally, obtain green bulk-shaped monocrystal, then with DMF washing, drying.
Sign to embodiment 1 title complex:
(1) powdery diffractometry characterizes phase purity (Fig. 2)
Powder diffraction data is collected on the Rigaku D/Max-2500 diffractometer and accomplishes, and instrumentation voltage is 40kV, and electric current is 100mA, uses the copper target X ray of graphite monochromatization.Scanning constant disperses that to depart from be 1 °, and receiving slit wide is 0.3 millimeter.Density data collect to be used 2 θ/θ scan pattern, and continuous sweep is accomplished in 3 ° to 80 ° scopes, and sweep velocity is 8 a °/per second, span be 0.02 °/each.Data fitting is used the Cerius2 program, and single crystal structure powdery diffractometry spectrum analog transforms and uses Mercury 1.4.2.
(2) crystal structure determination (Fig. 3,4)
Choose the monocrystalline of suitable size at microscopically; T=113K uses through the Mo-K of graphite monochromator monochromatization alpha-ray
and collects diffraction data with
mode on Rigaku RAXIS-RAPID diffractometer under the low temperature.All diffraction datas use the SADABS program to carry out absorption correction.Unit cell parameters is confirmed with method of least squares.Reduction of data and structure elucidation use SAINT and SHELXTL program to accomplish respectively.Earlier confirm whole non-hydrogen atom coordinates, and obtain the Wasserstoffatoms position of main body framework, with method of least squares crystalline structure is carried out refine then with theoretical hydrogenation method with difference functions method and method of least squares.Structure is seen Fig. 3 and 4.The partial parameters of data gathering of crystallography point diffraction and structure refinement is listed in following table.
Ligand polymer { [Ni (L) (PTA)] (DMF)
2.5}
nExperiment of main crystallography and refine parameter
Study on adsorption properties to embodiment 1 title complex:
N
2(77K) and H
2(77K) adsorption experiment uses full-automatic specific surface area of Micromeritics ASAP 2020M and the completion of lacunarity analysis instrument apparatus that Micromeritics Instrument Corp. U.S.A produces.Use high-purity gas, 101.0 milligrams { [Ni (L) (PTA)] (DMF)
2.5}
nSample is recycled and accomplishes all tests.The result sees Fig. 5.
Claims (9)
1. micropore nickel ligand polymer is characterized in that it is the compound of following chemical formula: { [Ni (L) (PTA)] (DMF)
2.5}
n, wherein L is 1,3,5-three (p-imidazoles phenyl) benzene, and PTA is a terephthalic acid, DMF is N, dinethylformamide; Main infrared absorption peak is 3128cm
-1, 1666cm
-1, 1606cm
-1, 1575cm
-1, 1523cm
-1, 1385cm
-1, 1308cm
-1, 1065cm
-1, 964cm
-1, 819cm
-1, 753cm
-1, 662cm
-1
2. the described micropore nickel of claim 1 ligand polymer crystal belongs to oblique system, and spacer is P2
1/ n, unit cell parameters is:
α=γ=90 °, β=92.152 (5) °.
3. the described micropore nickel of claim 1 ligand polymer is characterized in that its structure is: ligand L and metallic nickel formation 6
3Two-dimensional network, part PTA is with 6 then
3Network is connected to form the three-dimensional micropore structure; Be filled with the solvent DMF molecule in the duct, channel diameter is about
One-piece construction is double IPN gra topology network architecture.
4. the described micropore nickel of claim 1 ligand polymer, the decomposition temperature that it is characterized in that the coordination main body framework of ligand polymer is 348 ℃.
5. the preparation method of the described micropore nickel of claim 1 coordination polymer material is characterized in that it comprises the steps:
(1) with organic ligand L, terephthalic acid, nickelous nitrate and pyridine join N, in the dinethylformamide solvent;
(2) the DMF mixing solutions in the step 1 is obtained block green monocrystalline through solvent thermal reaction, then with DMF washing, drying.
6. according to the preparation method of the said micropore nickel of claim 5 coordination polymer material, it is characterized in that described L and PTA mol ratio are 1: 2～1: 3.
7. according to the preparation method of the said micropore nickel of claim 5 coordination polymer material, the mol ratio that it is characterized in that described L and nickelous nitrate is 1: 1～1: 2.5.
8. according to the preparation method of the said micropore nickel of claim 5 coordination polymer material, the solvent thermal condition that it is characterized in that said thermal response is for slowly dropping to room temperature in insulation under 115～125 ℃ after 5 days.
9. the application of the said micropore nickel of claim 1 coordination polymer material is characterized in that polymkeric substance has the character of selective adsorption gas, is applied to the material of divided gas flow.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204883A (en) * | 2013-04-19 | 2013-07-17 | 南开大学 | Cobalt coordination polymer with reversible monocrystal-monocrystal transformation behavior |
| CN103450234A (en) * | 2013-07-29 | 2013-12-18 | 南开大学 | Cadmium coordination polymer and preparation method thereof |
| CN105503734A (en) * | 2016-01-22 | 2016-04-20 | 辽宁大学 | Coordination polymer constructed based on nitrogenous ligand and synthesis method and application thereof |
| CN107474060A (en) * | 2017-08-11 | 2017-12-15 | 南开大学 | It is a kind of have be selectively adsorbing and separating metal-organic framework material of anionic dye performance and its preparation method and application |
| CN105753845B (en) * | 2016-03-14 | 2018-07-31 | 北京工业大学 | A kind of metal-organic framework materials and preparation method thereof based on low symmetrical four teeth Pyrazole Ligands Ni |
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| CN101531671A (en) * | 2009-04-15 | 2009-09-16 | 南开大学 | Micro-porous copper coordination polymer, preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204883A (en) * | 2013-04-19 | 2013-07-17 | 南开大学 | Cobalt coordination polymer with reversible monocrystal-monocrystal transformation behavior |
| CN103204883B (en) * | 2013-04-19 | 2015-10-07 | 南开大学 | A kind of cobalt coordination polymer with reversible monocrystalline-monocrystalline conversion behavior |
| CN103450234A (en) * | 2013-07-29 | 2013-12-18 | 南开大学 | Cadmium coordination polymer and preparation method thereof |
| CN103450234B (en) * | 2013-07-29 | 2016-05-04 | 南开大学 | A kind of cadmium coordination polymer and preparation method thereof |
| CN105503734A (en) * | 2016-01-22 | 2016-04-20 | 辽宁大学 | Coordination polymer constructed based on nitrogenous ligand and synthesis method and application thereof |
| CN105753845B (en) * | 2016-03-14 | 2018-07-31 | 北京工业大学 | A kind of metal-organic framework materials and preparation method thereof based on low symmetrical four teeth Pyrazole Ligands Ni |
| CN107474060A (en) * | 2017-08-11 | 2017-12-15 | 南开大学 | It is a kind of have be selectively adsorbing and separating metal-organic framework material of anionic dye performance and its preparation method and application |
| CN107474060B (en) * | 2017-08-11 | 2019-05-17 | 南开大学 | It is a kind of with the metal-organic framework materials and its preparation method and application for being selectively adsorbing and separating anionic dye performance |
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