CN106188109A - The double triazole two dimension cadmium complex monocrystalline of 1,4 dibromo 2,5 dimethylenes and application - Google Patents

The double triazole two dimension cadmium complex monocrystalline of 1,4 dibromo 2,5 dimethylenes and application Download PDF

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CN106188109A
CN106188109A CN201610602762.8A CN201610602762A CN106188109A CN 106188109 A CN106188109 A CN 106188109A CN 201610602762 A CN201610602762 A CN 201610602762A CN 106188109 A CN106188109 A CN 106188109A
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triazole
btca
cadmium complex
monocrystalline
bromo
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王中良
尚云涛
张志罡
杨曦
郭长城
王英
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Tianjin University
Tianjin Normal University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005Reversible 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
    • C01B3/001Reversible 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
    • C01B3/0015Organic compounds; Solutions thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13Crystalline forms, e.g. polymorphs
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage

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Abstract

The invention discloses the double triazole two dimension cadmium complex monocrystalline of Isosorbide-5-Nitrae dibromo 2,5 dimethylene and application, its structure: [Cd (L)]2+[btca]2‑·H2O, wherein, L=4 (4 ((4H 1,2,4 triazole 4 base) methyl) 2,5 two bromomethyls) 4H 1,2,4 triazole;Btca=PMA.Also disclose the preparation method of monocrystalline simultaneously.It is to use room temperature volatility process, i.e. L, btca and Cd (NO3)2·6H2O filters after stirring half an hour in water, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X ray single crystal diffraction after volatilizing two weeks.Wherein L:btca:Cd (NO3)2·6H2The mol ratio of O is 1:1:1.The present invention further discloses the double triazole two dimension cadmium complex monocrystalline of 1,4 dibromo 2,5 dimethylenes as hydrogen storage material application in terms of adsorbed hydrogen.

Description

The double triazole two dimension cadmium complex monocrystalline of 1,4-bis-bromo-2,5-dimethylene and application
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 cadmium complex hydrogen storage material, be one in particular Plant the double triazole two dimension cadmium complex monocrystal coordination compound monocrystalline of 1,4-bis-bromo-2,5-dimethylene 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 use room temperature volatility process, i.e. L, btca and Cd (NO3)2·6H2O stirs mistake after half an hour in water Filter, filtrate room temperature obtains being suitable for the colourless bulk crystal structure of X-ray single crystal diffraction after volatilizing two weeks be [Cd (L)]2+[btca ]2-·H2O, wherein, L=4-(4-((4H-1,2,4-triazole-4-yls) methyl)-2,5-bis-bromomethyl)-4H-1,2,4-triazoles; Btca=PMA.Hydrogen can be adsorbed by this complex monocrystal as hydrogen storage material.
To this end, the invention discloses a kind of Isosorbide-5-Nitrae-two bromo-2, the monocrystalline of the double triazole two dimension cadmium complex of 5-dimethylene, its It is characterised by that this mono-crystalline structures uses APEX II CCD single crystal diffractometer, uses through graphite monochromatised Mok alpha ray, λ= 0.71073 is incident radiation, withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, Software is utilized to solve single crystal data from difference Fourier electron density map:
Its structure is as follows:
[Cd(L)]2+[btca]2-·H2O, wherein
L=4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,5-two bromomethyl)-4H-1,2,4-triazole;
Btca=PMA.
The present invention further discloses the preparation side of the double triazole two dimension cadmium complex monocrystalline of 1,4-bis-bromo-2,5-dimethylene Method, it is characterised in that it is to use room temperature volatility process, by L, btca and Cd (NO3)2·6H2O stirs mistake after half an hour in water Filter, filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks;Wherein L:btca:Cd (NO3)2·6H2The mol ratio of O is 1:1:1;
The structure of the double triazole two dimension cadmium complex monocrystalline of 1,4-bis-bromo-2,5-dimethylene is [Cd (L)]2+[btca]2-·H2O; Wherein L=4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,5-two bromomethyl)-4H-1,2,4-triazole;Btca=all Benzenetetracarboxylic acid;
L btca。
The present invention further discloses the double triazole two dimension cadmium complex monocrystalline of 1,4-bis-bromo-2,5-dimethylene as storage Hydrogen material is in preparation to the application in terms of hydrogen adsorption, and experimental result shows: anthracene nucleus double triazole two dimension cadmium coordination frame complex 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 and 1.38 wt%。
It is excellent that the double triazole two dimension cadmium complex monocrystalline of a kind of 1,4-bis-disclosed by the invention bromo-2,5-dimethylene is had Point 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) Isosorbide-5-Nitrae-two bromo-2 prepared by the present invention, the double triazole two dimension cadmium complex monocrystalline of 5-dimethylene, produce into This is low, and method is easy, is suitable for large-scale production.The double triazole two dimension cadmium complex monocrystalline conduct of 1,4-bis-bromo-2,5-dimethylene Hydrogen storage material has good application effect in terms of storing hydrogen.
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.Raw materials used it is commercially available.All raw materials are all public from chemical reagent both domestic and external The raw materials such as department buys, such as Isosorbide-5-Nitrae-two bromo-2,5-dimethyl benzene, through continuation purification but directly do not use.
Embodiment 1
The preparation of 4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,5-two bromomethyl)-4H-1,2,4-triazole (L)
1,4-bis-bromo-2,5-dimethyl benzene: the mol ratio of double formylhydrazines is 1:4
The bromo-2,5-of 1,4-bis-bis-it is separately added in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer Methylbenzene (1 mmol) and double formylhydrazine (4 mmol), start stirring 150oC, reacts 24 hours.After reaction terminates, will be anti- Answer liquid to be down to room temperature, the precipitation obtained added 100 mL hot methanols, after stirring and dissolving, filter, filtrate slowly volatilize obtain white Color solid, yield 85%.Elementary analysis (C12N6H10Br2) theoretical value (%): C, 36.21;H, 2.53;N, 21.11.Measured value: C, 36.24;H, 2.55;N, 21.05;
The double formylhydrazine of 1,4-bis-bromo-2,5-dimethyl benzene.
The preferred Isosorbide-5-Nitrae of the present invention-two bromo-2,5-dimethyl benzene: the mol ratio of double formylhydrazines is 1:4, reaction temperature 150 DEG C, 24 hours response time.Using " one kettle way ", by bromo-for Isosorbide-5-Nitrae-two 2,5-dimethyl benzene and double formylhydrazine are prepared in a heated condition 4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,5-two bromomethyl)-4H-1,2,4-triazole (L).
Embodiment 2
4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,5-two bromomethyl)-4H-1,2,4-triazole (L) (0.1 Mmol), PMA (btca) (0.1 mmol) and Cd (NO3)2·6H2O (0.1 mmol) is stirring half in water (10 mL) Filtering after hour, filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks.Productivity: 40%.Unit Element analyzes (C46H36Br6CdN18O9) theoretical value (%): C, 35.04;H, 2.30;N, 15.99.Measured value: C, 35.08;H, 2.34; N, 15.89.
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. an Isosorbide-5-Nitrae-two bromo-2, the monocrystalline of the double triazole two dimension cadmium complex of 5-dimethylene, it is characterised in that this mono-crystalline structures Using APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha ray, λ=0.71073 is incident spoke Penetrate, withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, from difference Fourier electronics Density map utilizes software to solve single crystal data:
Its structure is as follows:
[Cd(L)]2+[btca]2-·H2O, wherein L=4-(4-((4H-1,2,4-triazole-4-yls) methyl)-2,5-dibromo first Base)-4H-1,2,4-triazole;
Btca=PMA.
2. Isosorbide-5-Nitrae-two bromo-2 described in claim 1, the preparation method of the double triazole two dimension cadmium complex monocrystalline of 5-dimethylene, it is special Levy and be that it is to use room temperature volatility process, by L, btca and Cd (NO3)2·6H2O filters after stirring half an hour in water, and filtrate is normal Temperature volatilization obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after two weeks;Wherein L:btca:Cd (NO3)2·6H2O rubs That ratio is 1:1:1;
The structure of the double triazole two dimension cadmium complex monocrystalline of 1,4-bis-bromo-2,5-dimethylene is [Cd (L)]2+[btca]2-·H2O; Wherein L=4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,5-two bromomethyl)-4H-1,2,4-triazole;Btca=all Benzenetetracarboxylic acid;
L btca。
3. the double triazole two dimension cadmium complex monocrystalline of 1,4-bis-bromo-2,5-dimethylene described in claim 1 is as hydrogen storage material In preparation to the application in terms of hydrogen adsorption.
CN201610602762.8A 2016-07-28 2016-07-28 The double triazole two dimension cadmium complex monocrystalline of 1,4 dibromo 2,5 dimethylenes and application Pending CN106188109A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110358106A (en) * 2019-08-02 2019-10-22 湖北师范大学 A kind of anion frame metal-organic framework material and its preparation method and application of pair of nitro-aromatic explosive sensing

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524094A (en) * 2016-01-05 2016-04-27 天津师范大学 1, 4-dimethyl-2, 5-dimethylene bistriazole inclusion N, N'-diethyl acetamide cadmium complex single crystal
CN105541881A (en) * 2016-01-05 2016-05-04 天津师范大学 1,4-dimethyl-2,5-dimethylene bis(triazole) three-dimensional cadmium complex single crystal and application
CN105566361A (en) * 2016-01-05 2016-05-11 天津师范大学 1,4-dibromo-2,5-dimethylene bis(triazole) cadmium complex monocrystal and applications thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524094A (en) * 2016-01-05 2016-04-27 天津师范大学 1, 4-dimethyl-2, 5-dimethylene bistriazole inclusion N, N'-diethyl acetamide cadmium complex single crystal
CN105541881A (en) * 2016-01-05 2016-05-04 天津师范大学 1,4-dimethyl-2,5-dimethylene bis(triazole) three-dimensional cadmium complex single crystal and application
CN105566361A (en) * 2016-01-05 2016-05-11 天津师范大学 1,4-dibromo-2,5-dimethylene bis(triazole) cadmium complex monocrystal and applications thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110358106A (en) * 2019-08-02 2019-10-22 湖北师范大学 A kind of anion frame metal-organic framework material and its preparation method and application of pair of nitro-aromatic explosive sensing
CN110358106B (en) * 2019-08-02 2021-10-01 湖北师范大学 Anion framework metal organic framework material for sensing p-nitroaromatic explosives and preparation method and application thereof

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