CN106220658A - The double triazole two dimension cadmium complex monocrystalline of 1,2,4,5 durols and application - Google Patents
The double triazole two dimension cadmium complex monocrystalline of 1,2,4,5 durols and application Download PDFInfo
- Publication number
- CN106220658A CN106220658A CN201610602571.1A CN201610602571A CN106220658A CN 106220658 A CN106220658 A CN 106220658A CN 201610602571 A CN201610602571 A CN 201610602571A CN 106220658 A CN106220658 A CN 106220658A
- Authority
- CN
- China
- Prior art keywords
- triazole
- mipt
- dmf
- cadmium complex
- monocrystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
-
- 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
-
- 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
-
- 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 1,2,4, the double triazole cadmium complex monocrystalline of 5 durols and application, its structure: [Cd (L) (mipt) (DMF)], wherein, L=4 (4 ((4H 1,2,4 triazole 4 bases) methyl) 2,3,5,6 tetramethylphenyls) 4H 1,2,4 triazole；Methylresorcinol dioctyl phthalate between mipt=；DMF=N, N' dimethylformamide.Also disclose the preparation method of monocrystalline simultaneously.It is to use " room temperature volatility process ", i.e. L, mipt and Cd (NO3)2·6H2O filters after stirring half an hour in the mixed solvent of water and DMF, and filtrate room temperature obtains being suitable for the colourless bulk crystals of X ray single crystal diffraction after volatilizing two weeks.Wherein L:mipt:Cd (NO3)2·6H2The mol ratio of O is 1:1:1.The present invention further discloses the double triazole cadmium complex monocrystalline of 1,2,4,5 durols 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 cadmium complex hydrogen storage material, be one in particular
Plant the double triazole two dimension cadmium complex monocrystalline of 1,2,4,5-durol 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], phase
Close research and cause the extensive attention of countries in the world.American scientist Yaghi in 2003 etc. report micropore metal-organic frame
After MOF-5 has good hydrogen storage property [O. M. Yaghi etc.,Science2003, 300, 1127], metal-have
Machine frame hydrogen storage technology is increasingly becoming 21st century international emerging research frontier.
Summary of the invention
The present invention is i.e. to select Cd (NO3)2·6H2After O, mipt and L stir half an hour in the mixed solvent of water and DMF
Filtering, filtrate room temperature obtains being suitable for the water white transparency bulk crystals [Cd (L) (mipt) of X-ray single crystal diffraction after volatilizing one week
(DMF)] (1), (L=4-(4-((4H-1,2,4-triazole-4-yls) methyl)-2，3，5，6-tetramethylphenyl)-4H-1,2,4-
Triazole；A mipt=methylresorcinol dioctyl phthalate；DMF=N, N'-dimethylformamide).This complex monocrystal is as hydrogen storage material
Hydrogen can be adsorbed by material.
Following technical scheme is current inventor provides for this:
Its structure is as follows:
[Cd (L) (mipt) (DMF)], wherein
L=4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,3,5,6-tetramethylphenyl)-4H-1,2,4-triazole；
A mipt=methylresorcinol dioctyl phthalate；
DMF=N, N'-dimethylformamide.
The present invention further discloses the preparation method of the double triazole two dimension cadmium complex monocrystalline of 1，2，4，5-tetramethylbenzene, its
It is characterised by that it is to use room temperature volatility process, by L, mipt and Cd (NO3)2·6H2O stirs half in the mixed solvent of water and DMF
Filtering after hour, filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks；Wherein L:mipt:
Cd(NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole cadmium complex monocrystalline of 1,2,4,5-durol is [Cd (L) (mipt) (DMF)]；Wherein L=4-
(4-((4H-1,2,4-triazole-4-yl) methyl)-2,3,5,6-tetramethylphenyl)-4H-1,2,4-triazole；A mipt=methyl
M-phthalic acid；DMF=N, N'-dimethylformamide；
L mipt。
The present invention further discloses the double triazole two dimension cadmium complex monocrystalline of 1,2,4,5-durol as hydrogen storage material
Expecting in preparation the application in terms of hydrogen adsorption, experimental result shows: the double triazole cadmium complex monocrystalline of 1，2，4，5-tetramethylbenzene
Two dimension 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 is divided
0.87 and 1.38 wt% are not reached.
The double triazole cadmium complex monocrystalline have the advantage that of a kind of 1,2,4,5-durol disclosed by the invention and feature
It 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 two dimension cadmium complex monocrystalline of the 1，2，4，5-tetramethylbenzene prepared by the present invention, production cost is low,
Method is easy, is suitable for large-scale production.The double triazole cadmium complex monocrystalline of 1,2,4,5-durol 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 (4-(aminomethyl)-2,3,5,6-tetramethylphenyl) methylamine, 1H-
1,2,4-triazole, potassium carbonate, copper oxide, cadmium nitrate and a methylresorcinol dioctyl phthalate etc. are commercially available.
Embodiment 1
(4-(aminomethyl)-2,3,5,6-tetramethylphenyl) methylamine: the mol ratio of double formylhydrazines is 1:4
Be separately added in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer (4-(aminomethyl)-2,
3,5,6-tetramethylphenyls) methylamine (1 mmol) and double formylhydrazine (4 mmol), start stirring 150oC, reacts 24 hours.
After reaction terminates, reactant liquor is down to room temperature, the precipitation obtained is added 100 mL hot methanols, after stirring and dissolving, filter, filtrate
Slowly volatilization obtains white solid, yield 85%.Elementary analysis (C16N6H20) theoretical value (%): C, 64.84；H, 6.80；N,
28.36.Measured value: C, 64.88；H, 6.85；N, 28.05；
The double formylhydrazine of (4-(aminomethyl)-2,3,5,6-tetramethylphenyl) methylamine.
The mol ratio of the present invention preferably (4-(aminomethyl)-2,3,5,6-tetramethylphenyl) methylamine and double formylhydrazine is 1:4；
Reaction temperature 150 DEG C, 24 hours response time.Use " one kettle way ", by (4-(aminomethyl)-2，3，5，6-tetramethylphenyl) first
Amine and double formylhydrazine prepare 4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,3,5,6-durol in a heated condition
Base)-4H-1,2,4-triazole (L).
Embodiment 2
4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,3,5,6-tetramethylphenyl)-4H-1,2,4-triazole (L) (0.1
Mmol), methylresorcinol dioctyl phthalate (mipt) (0.1 mmol) and Cd (NO3)2·6H2O (0.1 mmol) is at water (10 mL)
Filtering after stirring half an hour in the mixed solvent of DMF (2 mL), filtrate room temperature obtains after volatilizing two weeks being suitable for X-ray monocrystalline
The colourless bulk crystals of diffraction.Productivity: 40%.Elementary analysis (C28H33CdN7O5) theoretical value (%): C, 50.95；H, 5.04；N,
14.86.Measured value: C, 51.05；H, 4.99；N, 14.82.
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 structure cell ginseng through least square refinement
Number, utilizes software 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 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 two dimension cadmium complex of 1，2，4，5-tetramethylbenzene, 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-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, from difference Fourier electron density
Desire to make money or profit and solve crystal structure with software, and through Lorentz lorentz and polarity effect correction, all of H atom is synthesized also by difference Fourier
Determine through preferable position calculation, detailed axonometry data:
Its structure is as follows:
[Cd (L) (mipt) (DMF)], wherein
L=4-(4-((4H-1,2,4-triazole-4-yl) methyl)-2,3,5,6-tetramethylphenyl)-4H-1,2,4-triazole；
A mipt=methylresorcinol dioctyl phthalate；
DMF=N, N'-dimethylformamide.
2. the preparation method of the double triazole two dimension cadmium complex monocrystalline of 1，2，4，5-tetramethylbenzene described in claim 1, its feature exists
It is to use room temperature volatility process, by L, mipt and Cd (NO in it3)2·6H2After O stirs half an hour in the mixed solvent of water and DMF
Filtering, filtrate room temperature obtains being suitable for the colourless bulk crystals of X-ray single crystal diffraction after volatilizing two weeks；Wherein L:mipt:Cd
(NO3)2·6H2The mol ratio of O is 1:1:1；
The structure of the double triazole cadmium complex monocrystalline of 1，2，4，5-tetramethylbenzene is [Cd (L) (mipt) (DMF)], wherein, L=4-
(4-((4H-1,2,4-triazole-4-yl) methyl)-2,3,5,6-tetramethylphenyl)-4H-1,2,4-triazole；A mipt=methyl
M-phthalic acid；DMF=N, N'-dimethylformamide；
L mipt。
3. the double triazole two dimension cadmium complex monocrystalline of 1,2,4,5-durol described in claim 1 as hydrogen storage material prepare right
Application in terms of hydrogen adsorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610602571.1A CN106220658A (en) | 2016-07-28 | 2016-07-28 | The double triazole two dimension cadmium complex monocrystalline of 1,2,4,5 durols and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610602571.1A CN106220658A (en) | 2016-07-28 | 2016-07-28 | The double triazole two dimension cadmium complex monocrystalline of 1,2,4,5 durols and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106220658A true CN106220658A (en) | 2016-12-14 |
Family
ID=57534429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610602571.1A Pending CN106220658A (en) | 2016-07-28 | 2016-07-28 | The double triazole two dimension cadmium complex monocrystalline of 1,2,4,5 durols and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106220658A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418654A (en) * | 2016-01-05 | 2016-03-23 | 天津师范大学 | 1,4-dimethyl-2,5-dimethylene bis(triazole) 5-methyl isophthalic acid cadimium complex single crystal and application |
| 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 |
| CN105524098A (en) * | 2016-01-05 | 2016-04-27 | 天津师范大学 | 1, 4-dimethyl-2, 5-dimethylene bistriazole isophthalic acid cadmium complex single crystal and application thereof |
| 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 |
| CN105622653A (en) * | 2016-01-05 | 2016-06-01 | 天津师范大学 | 1,4-dimethyl-2,5-dimethylene bistriazole terephthalic acid three-dimensional cadmium complex single crystal and application thereof |
-
2016
- 2016-07-28 CN CN201610602571.1A patent/CN106220658A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418654A (en) * | 2016-01-05 | 2016-03-23 | 天津师范大学 | 1,4-dimethyl-2,5-dimethylene bis(triazole) 5-methyl isophthalic acid cadimium complex single crystal and application |
| 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 |
| CN105524098A (en) * | 2016-01-05 | 2016-04-27 | 天津师范大学 | 1, 4-dimethyl-2, 5-dimethylene bistriazole isophthalic acid cadmium complex single crystal and application thereof |
| 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 |
| CN105622653A (en) * | 2016-01-05 | 2016-06-01 | 天津师范大学 | 1,4-dimethyl-2,5-dimethylene bistriazole terephthalic acid three-dimensional cadmium complex single crystal and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3514159B1 (en) | Aluminium metal organic framework material | |
| US6372932B1 (en) | Porous solid products of 1,3,5-benzenetricarboxylate and metal ions | |
| CN109776504A (en) | A kind of metal-organic framework material and preparation method and applications based on low symmetrical pyrazoles-Carboxylic acid ligand Zn | |
| JP2012528860A (en) | Porous crystalline materials, their synthesis and use | |
| Jacobsen et al. | Systematic investigations of the transition between framework topologies in Ce/Zr-MOFs | |
| Wong-Ng et al. | Improved synthesis and crystal structure of the flexible pillared layer porous coordination polymer: Ni (1, 2-bis (4-pyridyl) ethylene)[Ni (CN) 4] | |
| CN109851559B (en) | Nickel metal organic framework material based on double-end pyrazole ligand, and preparation method and application thereof | |
| CN106243137A (en) | The double triazole cadmium complex monocrystalline of 1,2,4,5 durols and application | |
| CN116496506A (en) | Preparation method and application of mesoporous crystalline material with super-large primary three-dimensional cage structure | |
| CN106220658A (en) | The double triazole two dimension cadmium complex monocrystalline of 1,2,4,5 durols and application | |
| CN106188109A (en) | The double triazole two dimension cadmium complex monocrystalline of 1,4 dibromo 2,5 dimethylenes and application | |
| CN106243133A (en) | There is the double triazole Zn complex monocrystalline of anthracene nucleus and the application of hydrogen adsorption character | |
| CN106220655A (en) | The double triazole trimesic acid Zn complex monocrystalline of 1,2,4,5 durols and application | |
| Lee et al. | A molecular porous zirconium–organic material exhibiting highly selective CO 2 adsorption, high thermal stability, reversible hydration, facile ligand exchange and exclusive dimerization of phenylacetylene | |
| CN106317127A (en) | Anthracene ring bis(triazole) isophthalic acid two-dimensional cobalt complex single crystal with hydrogen adsorption property and application | |
| US11311856B2 (en) | Vanadium metal-organic framework for selective adsorption | |
| CN106243156A (en) | The double triazole ferrous perchlorate's complex monocrystal of 4H thioether and application | |
| CN106220685A (en) | There is the double triazole two dimension manganese complex monocrystalline of anthracene nucleus and the application of hydrogen adsorption character | |
| CN106317089A (en) | 4H thioether bis(triazol 1 yl) cadmium complex single crystal and application thereof | |
| CN106188158A (en) | There is the double triazole M-phthalic acid nickel complex monocrystalline of anthracene nucleus and the application of hydrogen adsorption character | |
| CN106317088A (en) | 4H thioether bis(triazol 1 yl) three-dimensional cadmium complex single crystal and application thereof | |
| CN106188160A (en) | There is the double triazole three-dimensional nickel complex monocrystalline of anthracene nucleus and the application of hydrogen adsorption character | |
| CN106242965A (en) | 2,5 dibromo 1,4 benzene two epoxide zinc diacetate complex monocrystal and application | |
| CN106008567A (en) | 4H thioether bitriazole terephthalic acid two-dimensional zinc complex monocrystal and application | |
| CN106188159A (en) | There is the double triazole p-phthalic acid nickel complex monocrystalline of anthracene nucleus and the application of hydrogen adsorption character |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161214 |
|
| RJ01 | Rejection of invention patent application after publication |