CN106317128A - Anthracene ring bis(triazole) isophthalic acid cobalt nitrate complex single crystal with hydrogen adsorption property and application - Google Patents
Anthracene ring bis(triazole) isophthalic acid cobalt nitrate complex single crystal with hydrogen adsorption property and application Download PDFInfo
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- CN106317128A CN106317128A CN201610602683.7A CN201610602683A CN106317128A CN 106317128 A CN106317128 A CN 106317128A CN 201610602683 A CN201610602683 A CN 201610602683A CN 106317128 A CN106317128 A CN 106317128A
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- Prior art keywords
- triazole
- ipa
- single crystal
- cobalt nitrate
- 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 cobalt nitrate complex single crystal with the hydrogen adsorption property and application. The structure of the complex single crystal is [Co(L)(ipa)].0.5L.H2O, wherein L is 1-[9-(1H-1,2,4-triazole-1-yl)anthracene-10-yl]-1H-1,2,4-triazole, and ipa is isophthalic acid. Meanwhile, 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 water for half an hour and then filtered, filtrate volatilizes at normal temperature for a week, and the pink blocky 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 cobalt nitrate 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 cobalt nitrate 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 1/3rd of conventional metals hydride, uses
MOFs can be substantially reduced the weight of hydrogen storage device as hydrogen storage media.
This feature especially meets the hydrogen-feeding system requirement of hydrogen cell automobile.
In addition such material also has the feature that specific surface area is big, pore volume is big, is therefore that a kind of novel high-capacity is light
Matter hydrogen storage material, the hydrogen storage method the most having become a kind of novel simplicity arises at the historic moment.
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 thing
Reason absorption.
The Kitagawa etc. of Japan in 1997 reports the metal-organic framework that 4,4 '-bipyridyl constructs and has adsorbed gas
After the character of the little molecule of body [S. Kitagawa etc.,Angew. Chem. Int. Ed.1997, 36, 1725], it is correlated with and grinds
Study carefully the extensive attention causing countries in the world.
American scientist Yaghi in 2003 etc. report micropore metal-organic frame MOF-5 and have good hydrogen storage property
Afterwards [O. M. Yaghi etc.,Science2003, 300, 1127], metal-organic framework hydrogen storage technology is increasingly becoming 21
Century international emerging research frontier.
The present invention is i.e. to select Co (NO3)2·6H2O, ipa and L filter after stirring half an hour in water, and filtrate room temperature volatilizees
Obtain being suitable for pink bulk crystals [Co (L) (ipa)] the 0.5L H of X-ray single crystal diffraction after one week2O (1) (L =
1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；Ipa=M-phthalic acid).
Hydrogen can be adsorbed by this complex monocrystal as hydrogen storage material.
Summary of the invention
Following technical scheme is current inventor provides for this:
The double triazole M-phthalic acid cobalt nitrate 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)]·0.5L·H2O, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；Ipa=isophthalic two
Formic acid.
The present invention further discloses the preparation method of the double triazole M-phthalic acid cobalt nitrate 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 filter after stirring half an hour in water, filtrate
Room temperature obtains being suitable for the pink bulk crystals of X-ray single crystal diffraction after volatilizing one week；Wherein L, ipa and Co (NO3)2·6H2O
Mol ratio be 1:1:1；
The structure of the double triazole M-phthalic acid cobalt nitrate complex monocrystal of anthracene nucleus is [Co (L) (ipa)] 0.5L H2O；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 cobalt nitrate 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 nitrate two dimension coordination frame
Frame complex monocrystal is under about 3.4 MPa, and when 298 and 77 K, the hydrogen adsorption amount of this hydrogen storage Porous materials respectively reaches
0.87 and 1.38 wt%.
The double triazole M-phthalic acid cobalt nitrate 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 cobalt nitrate 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 cobalt nitrate complex monocrystal of anthracene nucleus has good as hydrogen storage material in terms of storing hydrogen
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 buy from chemical reagents corporation both domestic and external, through continuing
Purify but directly use.
Raw materials used 9,10-dibromoanthracene, 1H-1,2,4-triazole, potassium carbonate, copper oxide, cobalt nitrate and M-phthalic acid
Etc. being 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 being down to room temperature, filter, filtrate adds 100 mL water, separates out and precipitates in a large number, sucking filtration,
Collect 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 pink bulk crystals of applicable X-ray single crystal diffraction after volatilizing one week.
Productivity: 35%.
Elementary analysis (C35H24CoN9O5) theoretical value (%): C, 59.24；H, 3.41；N, 17.77 measured values: C, 59.15；
H, 3.22；N, 17.69.
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 atom 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 experiment carried out under 298 and 77 K is an adsorption process quickly, reaches within several seconds
Thermodynamical equilibrium, it is believed that this is physical adsorption process.
This adsorption process belongs to first kind gas absorption type, and this is also MOFs poromerics adsorption gas molecule most typically
One.
Hydrogen is located in duct, and the adsorbance that size limit in duct is one layer or which floor hydrogen molecule.
When about 3.4 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 cobalt nitrate coordination compound 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)]·0.5L·H2O, wherein
L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；
Ipa=M-phthalic acid.
2. the preparation method of the double triazole M-phthalic acid cobalt nitrate 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 filter after stirring half an hour in water, filtrate room temperature
Obtain being suitable for the pink bulk crystals of X-ray single crystal diffraction after volatilizing one week；Wherein, Co (NO3)2·6H2O, ipa and L's
Mol ratio is 1:1:1；
The structure of the double triazole M-phthalic acid cobalt nitrate complex monocrystal of anthracene nucleus is [Co (L) (ipa)] 0.5L H2O；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 cobalt nitrate 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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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 CN201610602683.7A patent/CN106317128A/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)》 * |
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Application publication date: 20170111 |