CN106243158A - There is the double triazole nickel complex monocrystalline of anthracene nucleus and the application of hydrogen adsorption character - Google Patents
There is the double triazole nickel complex monocrystalline of anthracene nucleus and the application of hydrogen adsorption character Download PDFInfo
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- CN106243158A CN106243158A CN201610602316.7A CN201610602316A CN106243158A CN 106243158 A CN106243158 A CN 106243158A CN 201610602316 A CN201610602316 A CN 201610602316A CN 106243158 A CN106243158 A CN 106243158A
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- triazole
- bpdc
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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
- C07F15/04—Nickel compounds
- C07F15/045—Nickel 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
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Abstract
The invention discloses the double triazole nickel complex monocrystalline of anthracene nucleus and application, its structure: [Ni (L) with hydrogen adsorption character2(bpdc)] 2DMAC, wherein, L=1 [9 (1H 1,2,4 triazole 1 base) anthracene 10 base] 1H 1,2,4 triazole, bpdc=4,4' biphenyl dicarboxylic acid；DMAC=N, N' dimethyl acetylamide.Also disclose the preparation method of monocrystalline simultaneously.It is to use " room temperature volatility process ", i.e. Ni (NO3)2·6H2O, bpdc and L filter after stirring half an hour in the mixed solvent of water and DMAC, and filtrate room temperature obtains being suitable for the green bulk crystals of X ray single crystal diffraction after volatilizing one week.Wherein Ni (NO3)2·6H2The mol ratio of O, bpdc and L is 1:1:1.The present invention further discloses the double triazole nickel complex monocrystalline of anthracene nucleus as hydrogen storage material application in terms of adsorbed hydrogen.
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 nickel complex hydrogen storage material, be one in particular
Plant the double triazole nickel complex monocrystalline 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 Ni (NO3)2·6H2After O, bpdc and L stir half an hour in the mixed solvent of water and DMAC
Filtering, filtrate room temperature obtains being suitable for the green bulk crystals [Ni (L) of X-ray single crystal diffraction after volatilizing one week2(bpdc)]·
2DMAC (1) (L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；bpdc = 4,
4'-biphenyl dicarboxylic acid；DMAC=N, N'-dimethyl acetylamide).Hydrogen can be entered by this complex monocrystal as hydrogen storage material
Row absorption.
Following technical scheme is current inventor provides for this:
The double triazole nickel complex monocrystalline of a kind of anthracene nucleus, it is characterised in that this mono-crystalline structures uses APEX II CCD single crystal diffraction
Instrument, uses through graphite monochromatised Mok alpha ray, and λ=0.71073 is incident radiation, withω-2θScan mode is collected and is spread out
Exit point, obtains cell parameter through least square refinement, utilizes SHELXL-97 direct method from difference Fourier electron density map
Solve single crystal data:
Its chemical constitution is as follows:
[Ni(L)2(bpdc)] 2DMAC, wherein
L=1-(2,5-dimethyl-4-(1H-1,2,4-triazol-1-yl) phenyl)-1H-1,2,4-triazole；
Bpdc=4,4'-biphenyl dicarboxylic acid；
DMAC=N, N'-dimethyl acetylamide.
The present invention further discloses the preparation method of the double triazole nickel complex monocrystalline of anthracene nucleus, it is characterised in that it is to use
" room temperature volatility process ", i.e. Ni (NO3)2·6H2O, bpdc and L filter after stirring half an hour in the mixed solvent of water and DMAC, filter
Liquid room temperature obtains being suitable for the green bulk crystals of X-ray single crystal diffraction after volatilizing one week；Wherein L, bpdc and Ni (NO3)2·
6H2The mol ratio of O is 1:1:1；
The structure of the double triazole nickel complex monocrystalline of anthracene nucleus is [Ni (L)2(bpdc)]·2DMAC；Wherein L=1-[9-(1H-1,2,
4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；Bpdc=4,4'-biphenyl dicarboxylic acid；DMAC=N, N'-bis-
Methylacetamide；
L bpdc。
The present invention further discloses the double triazole nickel complex monocrystalline of anthracene nucleus and inhales hydrogen in preparation as hydrogen storage material
The application in subsidiary formula face, experimental result shows: anthracene nucleus double triazole nickel three-dimensional coordination frame complex monocrystalline under about 3.4 MPa,
When 298 and 77 K, the hydrogen adsorption amount of this hydrogen storage Porous materials has respectively reached 0.87 and 1.38 wt%.
The double triazole nickel complex monocrystalline have the advantage that of a kind of anthracene nucleus disclosed by the invention and feature are:
(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 nickel complex monocrystalline of the anthracene nucleus prepared by the present invention, production cost is low, and method is easy, is suitable for big rule
Mould produces.The double triazole nickel complex monocrystalline of anthracene nucleus has good application effect as hydrogen storage material in terms of storing hydrogen.
Accompanying drawing explanation
The crystal structure figure of Fig. 1: complex monocrystal；
The tomograph 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, nickel nitrate and 4,4'-biphenyl dicarboxylic 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), 4,4'-biphenyl
Dioctyl phthalate (0.1 mmol) and Ni (NO3)2·6H2O (0.1 mmo) stirs in the mixed solvent of 10 mL water and 2 mL DMAC
Filtering after half an hour, filtrate is yellow.Room temperature has the green bulk crystals of applicable X-ray single crystal diffraction after volatilizing one week.Produce
Rate: 35%.Elementary analysis (C58H50N14NiO6) theoretical value (%): C, 63.46；H, 4.59；N, 17.86.Measured value: C, 63.47；
H, 4.52；N, 17.89.
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 metal-organic framework hydrogen storage Porous materials is as shown in Figure 3.The hydrogen adsorption carried out under 298 and 77 K is real
Testing is an adsorption process quickly, has reached thermodynamical equilibrium, it is believed that this is physical adsorption process within several seconds.
This adsorption process belongs to first kind gas absorption type, and this is also the MOFs most typical one of poromerics adsorption gas molecule.
Hydrogen is located in duct, and the adsorbance that size limit in duct is one layer or which floor hydrogen molecule.At about 3.4 MPa
During with 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 nickel complex of anthracene nucleus, it is characterised in that this mono-crystalline structures uses APEX II CCD monocrystalline to spread out
Penetrating instrument, use through graphite monochromatised Mok alpha ray, λ=0.71073 is incident radiation, withω-2θScan mode is collected
Point diffraction, obtains cell parameter through least square refinement, utilizes software to solve monocrystalline from difference Fourier electron density map
Data:
Its chemical constitution is as follows:
[Ni(L)2(bpdc)] 2DMAC, wherein
L=1-[9-(1H-1,2,4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；
Bpdc=4,4'-biphenyl dicarboxylic acid；DMAC=N, N'-dimethyl acetylamide.
2. the preparation method of the double triazole nickel complex monocrystalline of anthracene nucleus described in claim 1, it is characterised in that it is that " room temperature is waved in employing
The method of sending out ", i.e. i.e. Ni (NO3)2·6H2O, bpdc and L filter after stirring half an hour in the mixed solvent of water and DMAC, and filtrate is normal
Temperature volatilization obtains being suitable for the green bulk crystals of X-ray single crystal diffraction after one week；Wherein, Ni (NO3)2·6H2O, bpdc and L's
Mol ratio is 1:1:1；
The structure of the double triazole nickel complex monocrystalline of anthracene nucleus is [Ni (L)2(bpdc)]·2DMAC；Wherein L=1-[9-(1H-1,2,
4-triazole-1-base) anthracene-10-base]-1H-1,2,4-triazole；Bpdc=4,4'-biphenyl dicarboxylic acid；DMAC=N, N'-bis-
Methylacetamide；
L bpdc。
3. the double triazole nickel complex monocrystalline of anthracene nucleus described in claim 1 is answered in terms of preparation is to hydrogen adsorption as hydrogen storage material
With.
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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 CN201610602316.7A patent/CN106243158A/en active Pending
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| 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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