CN102584902A - Microporous cobalt coordination polymer and preparation method and application thereof - Google Patents

Microporous cobalt coordination polymer and preparation method and application thereof Download PDF

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CN102584902A
CN102584902A CN2012100066705A CN201210006670A CN102584902A CN 102584902 A CN102584902 A CN 102584902A CN 2012100066705 A CN2012100066705 A CN 2012100066705A CN 201210006670 A CN201210006670 A CN 201210006670A CN 102584902 A CN102584902 A CN 102584902A
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cobalt
micropore
tipb
adc
dmf
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卜显和
陈强
常泽
张大帅
宋伟朝
胡同亮
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Nankai University
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Abstract

The invention discloses a microporous cobalt coordination polymer and a preparation method and application thereof. The cobalt coordination polymer is a compound of the following chemical formula: [Co(tipb)(adc)](DMF)3(H2O)1.50, wherein tipb is 1,3,5-tri(p-imidazole phenyl) benzene, adc is p-9,10-anthracene diacid, and DMF is N,N-dimethyl formamide. The compound is prepared by adopting a solvent thermal method, and the obtained crystal has high purity. After free solvent molecules are removed, the microporous cobalt coordination polymer displays one-dimensional nano pore canals in the c-axis direction of the crystal. The coordination polymer can adsorb a large quantity of carbon dioxide but adsorb little nitrogen, oxygen and methane, achieves a good gas separation effect, can be used as a gas adsorption and separation agent, and has potential application value in the field of material science.

Description

Micropore cobalt ligand polymer and preparation method and application thereof
Technical field
The present invention relates to micropore metal-organic coordination polymer material; Particularly a kind of preparation method of cobalt ligand polymer and application thereof; Described cobalt ligand polymer is the Co-1 with micropore, 3, and 5-three (p-imidazoles phenyl) benzene-9; The polymkeric substance of 10-anthracene diacid three-dimensional net structure has stronger selective adsorption function to carbonic acid gas.
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 particularly has selective adsorption gas materials with function.This is because the duct size of this base polymer material has strict restriction and requires it that good stability is arranged.It is to utilize compound duct unique characteristics that a kind of method is arranged, in conjunction with factors such as the quadrupole moment of all gases molecule, polarizabilities, can active adsorption and the duct gas molecule than strong interaction is arranged, 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: Pan, L.; Olson, D.H.; Ciemnolonski, L.R.; Heddy, R.; Li, J.Angew.Chem.Int.Ed.2006,118,632; Zou, Y.; Hong, S.; Park, M.; Chun, H; Lah, M.S.Chem.Commun.2007,5182; 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 cobalt ligand polymer and preparation and application thereof; This material is the Co-1 with one-dimensional channels; 3; 5-three (p-imidazoles phenyl) benzene-9, the polymkeric substance of 10-anthracene diacid three-dimensional net structure, its coordination skeleton have stronger selective adsorption performance to carbonic acid gas and methane nitrogen oxygen under 195K and 273K condition.
The chemical formula of micropore cobalt ligand polymer of the present invention be [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50, wherein tipb is 1,3,5-three (p-imidazoles phenyl) benzene, and adc is to 9,10-anthracene diacid, DMF are N, dinethylformamide; Main infrared absorption peak is 3134cm -1, 1664cm -1, 1598cm -1, 1521cm -1, 1400cm -1, 1309cm -1, 1061cm -1, 963cm -1, 833cm -1, 656cm -1
The decomposition temperature of micropore cobalt ligand polymer coordination main body framework of the present invention is 300 ℃.Micropore cobalt ligand polymer crystal of the present invention belongs to oblique system, and spacer is C2/c, and unit cell parameters is:
Figure BSA00000655720100022
Figure BSA00000655720100023
Figure BSA00000655720100024
α=γ=90 °, β=103.206 (4) °; Its structure is: part tipb and cobalt metal form 6 3Two-dimensional network, part adc is with 6 then 3Network is connected to form the three-dimensional micropore structure; Be filled with solvent DMF and water molecules in the duct; One-piece construction is the gra network topology structure.
The duct of micropore cobalt ligand polymer of the present invention is 1-dimention nano size duct on the c direction, and the duct size is about 0.96 * 0.73nm.
The compound method of micropore cobalt ligand polymer of the present invention may further comprise the steps:
With organic ligand tipb, adc, Xiao Suangu 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.
Described tipb and adc mol ratio are 1: 1～1: 1.5.
The mol ratio of described tipb and Xiao Suangu is 1: 1～1: 2.5.
The solvent thermal condition of said thermal response is to react 3 days down at 155～165 ℃, 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 its absorbing carbon dioxide gas more in large quantities under 195K and 273K, but similarity condition adsorbs methane nitrogen oxygen 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 [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50Thermogram;
Fig. 2 [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50The alternating temperature powder diagram;
Fig. 3 [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50Powder diagram;
Fig. 4 [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50Mode of connection figure;
Fig. 5 [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50Three-dimensional net structure figure;
Fig. 6 [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50195K gas adsorption figure;
Fig. 7 [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50273K gas 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 milligram), 9,10-anthracene diacid (0.1 mmole; Cobaltous nitrate hexahydrate (0.1 mmole, 29.1 milligrams) and 2 of pyridines are dissolved in 10 milliliters of N 26.6 milligram); In the dinethylformamide solvent, this DMF is mixed the molten solvent thermal reaction still of packing into.Reacted 3 days down at 160 ℃, reduce to room temperature, obtain red bulk-shaped monocrystal, then with DMF washing, drying with 0.1 ℃/min speed.
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. 4,5)
Choose the monocrystalline of suitable size at microscopically; T=113K uses through the Mo-K of graphite monochromator monochromatization alpha-ray
Figure BSA00000655720100031
and collects diffraction data with
Figure BSA00000655720100032
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 Figure 4 and 5.The partial parameters of data gathering of crystallography point diffraction and structure refinement is listed in following table.
Ligand polymer [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50Experiment of main crystallography and refine parameter
Figure BSA00000655720100041
Study on adsorption properties to embodiment 1 title complex:
Full-automatic specific surface area of Micromeritics ASAP 2020M and lacunarity analysis instrument apparatus that the gas adsorption experiment uses Micromeritics Instrument Corp. U.S.A to produce are accomplished.Use high-purity gas, 98.7 milligrams [Co (tipb) (adc)] are (DMF) 3(H 2O) 1.50Sample is recycled and accomplishes all tests.The result sees Fig. 6, Fig. 7.

Claims (10)

1. micropore cobalt ligand polymer is characterized in that it is the compound of following chemical formula: [Co (tipb) (adc)] (DMF) 3(H 2O) 1.50, wherein tipb is 1,3,5-three (p-imidazoles phenyl) benzene, and adc is to 9,10-anthracene diacid, DMF are N, dinethylformamide; Main infrared absorption peak is 3134cm -1, 1664cm -1, 1598cm -1, 1521cm -1, 1400cm -1, 1309cm -1, 1061cm -1, 963cm -1, 833cm -1, 656cm -1
2. the described micropore cobalt of claim 1 ligand polymer crystal belongs to oblique system; Spacer is C2/c; Unit cell parameters is:
Figure FSA00000655700000011
α=γ=90 °, β=103.206 (4) °.
3. the described micropore cobalt of claim 1 ligand polymer is characterized in that its structure is: part tipb and cobalt metal formation 6 3Two-dimensional network, part adc is with 6 then 3Network is connected to form the three-dimensional micropore structure; Be filled with solvent DMF and water molecules in the duct; One-piece construction is the gra network topology structure.
4. the described micropore cobalt of claim 1 ligand polymer, the decomposition temperature that it is characterized in that the coordination main body framework of ligand polymer is 300 ℃.
5. the described micropore cobalt of claim 1 ligand polymer, the duct that it is characterized in that ligand polymer is 1-dimention nano size duct on the c direction, the duct size is about 0.96 * 0.73nm.
6. the preparation method of the described micropore cobalt of claim 1 coordination polymer material is characterized in that it comprises the steps:
(1) with organic ligand tipb, adc, Xiao Suangu and pyridine join N, in the dinethylformamide solvent;
(2) the DMF mixing solutions in the step 1 is obtained block red monocrystalline through solvent thermal reaction, then with DMF washing, drying.
7. according to the preparation method of the said micropore cobalt of claim 6 coordination polymer material, it is characterized in that described tipb and adc mol ratio are 1: 1～1: 1.5.
8. according to the preparation method of the said micropore cobalt of claim 6 coordination polymer material, the mol ratio that it is characterized in that described tipb and Xiao Suangu is 1: 1～1: 2.5.
9. according to the preparation method of the said micropore cobalt of claim 6 coordination polymer material, the solvent thermal condition that it is characterized in that said thermal response slowly drops to room temperature for reacting 3 days down at 155～165 ℃.
10. the application of the said micropore cobalt 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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CN103204883A (en) * 2013-04-19 2013-07-17 南开大学 Cobalt coordination polymer with reversible monocrystal-monocrystal transformation behavior
CN103275286A (en) * 2013-06-21 2013-09-04 南开大学 Preparation method and application of selective adsorptive separation porous organic polymer material
CN103450234A (en) * 2013-07-29 2013-12-18 南开大学 Cadmium coordination polymer and preparation method thereof
CN103951708A (en) * 2014-04-18 2014-07-30 海南大学 Multidentate carboxylic acid coordination polymer and preparation method thereof
CN106589394A (en) * 2016-10-19 2017-04-26 南京科技职业学院 Cobalt coordination polymer and preparation method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
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
CN103275286A (en) * 2013-06-21 2013-09-04 南开大学 Preparation method and application of selective adsorptive separation porous organic polymer material
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
CN103951708A (en) * 2014-04-18 2014-07-30 海南大学 Multidentate carboxylic acid coordination polymer and preparation method thereof
CN106589394A (en) * 2016-10-19 2017-04-26 南京科技职业学院 Cobalt coordination polymer and preparation method thereof
CN106589394B (en) * 2016-10-19 2019-04-05 南京科技职业学院 A kind of cobalt coordination polymer and preparation method thereof

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