CN106317127A - Anthracene ring bis(triazole) isophthalic acid two-dimensional cobalt complex single crystal with hydrogen adsorption property and application - Google Patents
Anthracene ring bis(triazole) isophthalic acid two-dimensional cobalt complex single crystal with hydrogen adsorption property and application Download PDFInfo
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- CN106317127A CN106317127A CN201610602335.XA CN201610602335A CN106317127A CN 106317127 A CN106317127 A CN 106317127A CN 201610602335 A CN201610602335 A CN 201610602335A CN 106317127 A CN106317127 A CN 106317127A
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- triazole
- ipa
- single crystal
- cobalt complex
- phthalic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses an anthracene ring bis(triazole) isophthalic acid two-dimensional cobalt complex single crystal with the hydrogen adsorption property and application. The structure of the single crystal is [Co(L)(ipa)].DMF, wherein L is 1-[9-(1H-1,2,4-triazole-1-yl)anthracene-10-yl]-1H-1,2,4-triazole, ipa is isophthalic acid, and DMF is N,N'-dimethylformamide. The invention further discloses a preparation method of the single crystal. A normal-temperature volatilization method is adopted, that is, Co(NO3)2.6H2O, ipa and L are stirred in a mixed solvent of water and DMF for half an hour and then filtered, filtrate volatilizes at normal temperature for a week, and the rufous clustered crystal suitable for X-ray single crystal diffraction is obtained, wherein the molar ratio of Co(NO3)2.6H2O to ipa to L is 1:1:1. The invention further discloses application of the anthracene ring bis(triazole) isophthalic acid two-dimensional cobalt complex single crystal to hydrogen adsorption as a hydrogen storage material.
Description
The present invention obtains the subsidy of Tianjin innovation team of Education Commission (TD12-5037).
Technical field
The present invention relates to the preparation method and applications of triazole organic acid cobalt complex hydrogen storage material, be one in particular
Plant the double triazole M-phthalic acid two dimension cobalt complex monocrystal of anthracene nucleus and application.
Background technology
The synthesis of metal-organic framework (MOFs) and character research are the nothings that nineteen nineties Later development gets up
One of important field of research in chemical machine and materials chemistry.Owing to open metal-organic coordination polymer density is little, it is only
/ 3rd of conventional metals hydride, use MOFs can be substantially reduced the weight of hydrogen storage device as hydrogen storage media.This feature
Especially meet the hydrogen-feeding system requirement of hydrogen cell automobile.In addition such material also has that specific surface area is big, pore volume is big
Feature, be therefore a kind of novel high-capacity light hydrogen occluding material, the hydrogen storage method the most having become a kind of novel simplicity should
Transport and give birth to.It is, in general, that hydrogen storage mechanism can be divided into chemisorbed and physical absorption, and the hydrogen storage mechanism of coordination compound is mostly physics
Absorption.The Kitagawa etc. of Japan in 1997 reports the metal-organic framework that 4,4 '-bipyridyl constructs, and to have adsorbed gas little
After the character of molecule [S. Kitagawa etc.,Angew. Chem. Int. Ed.1997, 36, 1725], correlational study draws
Play the extensive attention of countries in the world.American scientist Yaghi in 2003 etc. report micropore metal-organic frame MOF-5 tool
After having good hydrogen storage property [O. M. Yaghi etc.,Science2003, 300, 1127], metal-organic framework hydrogen storage skill
Art is increasingly becoming 21st century international emerging research frontier.
Summary of the invention
The present invention is i.e. to select Co (NO3)2·6H2O, ipa and L stir mistake after half an hour in the mixed solvent of water and DMF
Filter, filtrate room temperature obtains being suitable for bronzing tufted crystal [Co (L) (the ipa)] DMF of X-ray single crystal diffraction after volatilizing one week
(1) (L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；Ipa=isophthalic diformazan
Acid, DMF=N, N'-dimethylformamide).Hydrogen can be adsorbed by this complex monocrystal as hydrogen storage material.
Following technical scheme is current inventor provides for this:
The double triazole M-phthalic acid two dimension cobalt complex monocrystal of a kind of anthracene nucleus, it is characterised in that this mono-crystalline structures uses APEX II
CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ=0.71073 is incident radiation, withω-2θSweep
The mode of retouching collects point diffraction, obtains cell parameter through least square refinement, utilizes from difference Fourier electron density map
SHELXL-97 direct method solves single crystal data:
Its chemical constitution is as follows:
[Co (L) (ipa)] DMF, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Ipa=M-phthalic acid；
DMF=N, N'-dimethylformamide.
The present invention further discloses the preparation method of the double triazole M-phthalic acid two dimension cobalt complex monocrystal of anthracene nucleus, it is special
Levy and be that it is to use " room temperature volatility process ", i.e. Co (NO3)2·6H2O, ipa and L stir half in the mixed solvent of water and DMF
Filtering after hour, filtrate room temperature obtains being suitable for the bronzing tufted crystal of X-ray single crystal diffraction after volatilizing one week；Wherein L, ipa
With Co (NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole M-phthalic acid two dimension cobalt complex monocrystal of anthracene nucleus is [Co (L) (ipa)] DMF；Wherein L=1-
[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；Ipa=M-phthalic acid；
L ipa。
The present invention further discloses the double triazole M-phthalic acid two dimension cobalt complex monocrystal of anthracene nucleus as hydrogen storage material
In preparation to the application in terms of hydrogen adsorption, experimental result shows: anthracene nucleus double triazole M-phthalic acid cobalt two dimension coordination framework is joined
Compound monocrystalline is under about 3.4 MPa, and when 298 and 77 K, the hydrogen adsorption amount of this hydrogen storage Porous materials has respectively reached 0.87 He
1.38 wt%。
The double triazole M-phthalic acid two dimension cobalt complex monocrystal have the advantage that of a kind of anthracene nucleus disclosed by the invention and spy
Point is:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) the double triazole M-phthalic acid two dimension cobalt complex monocrystal of the anthracene nucleus prepared by the present invention, production cost is low, side
Method is easy, is suitable for large-scale production.The double triazole M-phthalic acid two dimension cobalt complex monocrystal of anthracene nucleus is storing as hydrogen storage material
Hydrogen aspect has good application effect.
Accompanying drawing explanation
The crystal structure figure of Fig. 1: complex monocrystal；
The two-dimensional structure figure of Fig. 2: complex monocrystal；
Fig. 3: inhale hydrogen curve.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and embodiment is only explanatory, is in no way intended to it
Limit the scope of the present invention by any way.All of raw material is such as: anthracene nucleus etc. are all to enter from chemical reagents corporation both domestic and external
Row is bought, and through continuation purification but does not directly use.Raw materials used 9,10-dibromoanthracene, 1H-1,2,4-triazole, carbon
Acid potassium, copper oxide, cobalt nitrate and M-phthalic acid etc. are commercially available.
Embodiment 1
9,10-dibromoanthracene: 1H-1,2,4-triazole: potassium carbonate: the mol ratio of copper oxide is 2:10-15:30:1
Be separately added in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer CuO (0.0398 mg,
0.5 mmol), potassium carbonate (2.0731 g, 15 mmol), triazole (0.345 mg, 5 mmol), 9,10-dibromoanthracenes (0.3360
G, 1 mmol), 20 mL DMF.Start stirring 100oC, reacts 24 hours.After reaction terminates, reactant liquor is down to room temperature,
Filtering, filtrate adds 100 mL water, separates out a large amount of precipitation, sucking filtration, collects filter cake, yield 60%.
Embodiment 2
1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole (0.1 mmol), isophthalic diformazan
Acid (0.1 mmol) and Co (NO3)2·6H2O (0.1 mmo) filters after stirring half an hour in 10 mL water, and filtrate is reddish brown
Color.Room temperature has the bronzing bulk crystals of applicable X-ray single crystal diffraction after volatilizing one week.Productivity: 35%.Elementary analysis
(C58H46Co2N14O10) theoretical value (%): C, 57.24；H, 3.81；N, 16.11.Measured value: C, 57.34；H, 3.72；N,
16.29。
Embodiment 3
Crystal structure determination uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ=
0.71073 is incident radiation, withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement,
Software is utilized to solve crystal structure from difference Fourier electron density map, and through Lorentz lorentz and polarity effect correction.All of H is former
Son is synthesized by difference Fourier and determines through preferable position calculation.Detailed axonometry data:
Embodiment 4
The suction hydrogen curve of this metal-organic framework hydrogen storage Porous materials is as shown in Figure 3.The hydrogen adsorption carried out under 298 and 77 K
Experiment is an adsorption process quickly, has reached thermodynamical equilibrium within several seconds, it is believed that this is physical absorption
Journey.This adsorption process belongs to first kind gas absorption type, and this is also MOFs poromerics adsorption gas molecule most typical
Kind.Hydrogen is located in duct, and the adsorbance that size limit in duct is one layer or which floor hydrogen molecule.About 3.4
During MPa and 77 K, the adsorbance of hydrogen has reached 1.38 wt%.
After the preferred embodiment described in detail, it is familiar with this skilled worker and is clearly understood that, without departing from above-mentioned
Can carry out various change and amendment under claim and spirit, all technical spirit according to the present invention are to above example institute
Any simple modification, equivalent variations and the modification made, belongs to the scope of technical solution of the present invention.And the present invention is not illustrated
The restriction of example embodiment in book.
Claims (3)
1. the monocrystalline of the double triazole M-phthalic acid two dimension cobalt complex of anthracene nucleus, it is characterised in that this mono-crystalline structures uses APEX
II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, and λ=0.71073 is incident radiation, withω-2θ
Scan mode collects point diffraction, obtains cell parameter through least square refinement, utilizes from difference Fourier electron density map
Software solves single crystal data:
Its chemical constitution is as follows:
[Co (L) (ipa)] DMF, wherein
L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；
Ipa=M-phthalic acid；DMF=N, N'-dimethylformamide.
2. the preparation method of the double triazole M-phthalic acid two dimension cobalt complex monocrystal of anthracene nucleus described in claim 1, it is characterised in that
It is to use " room temperature volatility process ", i.e. i.e. Co (NO3)2·6H2O, ipa and L stir half an hour in the mixed solvent of water and DMF
Rear filtration, filtrate room temperature obtains being suitable for the bronzing tufted crystal of X-ray single crystal diffraction after volatilizing one week；Wherein, Co
(NO3)2·6H2The mol ratio of O, ipa and L is 1:1:1；
The structure of the double triazole M-phthalic acid two dimension cobalt complex monocrystal of anthracene nucleus is [Co (L) (ipa)] DMF；Wherein L=1-
[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；Ipa=M-phthalic acid；
L ipa。
3. the double triazole M-phthalic acid two dimension cobalt complex monocrystal of anthracene nucleus described in claim 1 is being prepared hydrogen as hydrogen storage material
The application in aspiration subsidiary formula face.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539325A (en) * | 2022-03-16 | 2022-05-27 | 合肥工业大学 | Preparation and application of benzotriazole cobalt complex |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418647A (en) * | 2016-01-05 | 2016-03-23 | 天津师范大学 | Anthracene nucleus di-triazole three-dimensional copper nitrate complex single crystal and application |
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- 2016-07-28 CN CN201610602335.XA patent/CN106317127A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418647A (en) * | 2016-01-05 | 2016-03-23 | 天津师范大学 | Anthracene nucleus di-triazole three-dimensional copper nitrate complex single crystal and application |
Non-Patent Citations (2)
| Title |
|---|
| 纪穆为等，: "金属有机框架化合物_MOFs_的研究状况", 《山东化工》 * |
| 许春慧等，: "金属有机骨架材料上气体吸附存储与分离的研究进展", 《浙江师范大学学报( 自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114539325A (en) * | 2022-03-16 | 2022-05-27 | 合肥工业大学 | Preparation and application of benzotriazole cobalt complex |
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Application publication date: 20170111 |