CN106317089A - 4H thioether bis(triazol 1 yl) cadmium complex single crystal and application thereof - Google Patents
4H thioether bis(triazol 1 yl) cadmium complex single crystal and application thereof Download PDFInfo
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- CN106317089A CN106317089A CN201610602389.6A CN201610602389A CN106317089A CN 106317089 A CN106317089 A CN 106317089A CN 201610602389 A CN201610602389 A CN 201610602389A CN 106317089 A CN106317089 A CN 106317089A
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- cadmium complex
- thioether
- single crystal
- monocrystalline
- triazol
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- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 20
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 title claims abstract description 20
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 20
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 title abstract 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011232 storage material Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003852 triazoles Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 238000003860 storage Methods 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- GBBFUAZDRBBUQG-UHFFFAOYSA-N N=1N=CN(C=1)C1=CC=C(C=C1)[S] Chemical compound N=1N=CN(C=1)C1=CC=C(C=C1)[S] GBBFUAZDRBBUQG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 metals hydride Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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 Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a 4H thioether bis(triazol 1 yl) cadmium complex single crystal and application thereof. The 4H thioether bis(triazol 1 yl) cadmium complex single crystal has the following structure: [Cd (H2O) 2 (L) 4].7H2O, wherein L=bi(4-(4H-1, 2, 4-triazole-4-group)phenyl)sulfur. The invention further discloses a preparation method for the 4H thioether bis(triazol 1 yl) cadmium complex single crystal. A normal temperature evaporation method is adopted, and comprises the following steps of stirring L and Cd(NO3)2.6H2O in water for half an hour, filtering, volatilizing the filtrate at normal temperature for two weeks to obtain colorless block crystals suitable for X ray single crystal diffraction. The molar ratio of L:Cd(NO3)2.6H2O is 1:1. The invention further discloses application of 4H thioether bis(triazol 1 yl) cadmium complex single crystal used as hydrogen storage materials in the hydrogen adsorption.
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 the double triazole cadmium complex hydrogen storage material of 4H thioether, be in particular
The double triazole cadmium complex monocrystalline of a kind of 4H thioether 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 and Cd (NO3)2·6H2O filters after stirring half an hour in water, filter
Liquid room temperature obtains being suitable for the colourless bulk crystal structure of X-ray single crystal diffraction after volatilizing two weeks be [Cd (H2O)2(L)4]·
7H2O, wherein, L=bis-(4-(4H-1,2,4-triazole-4-yls) phenyl) sulfur.This complex monocrystal can be right as hydrogen storage material
Hydrogen adsorbs.
To this end, the invention discloses the monocrystalline of the double triazole cadmium complex of a kind of 4H thioether, 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(H2O)2(L)4]·7H2O, wherein
L=bis-(4-(4H-1,2,4-triazole-4-yl) phenyl) sulfur.
The present invention further discloses the preparation method of the double triazole cadmium complex monocrystalline of 4H thioether, it is characterised in that it is to adopt
Use room temperature volatility process, by L and Cd (NO3)2·6H2O filters after stirring half an hour in water, and filtrate room temperature obtains after volatilizing two weeks
It is suitable for the colourless bulk crystals of X-ray single crystal diffraction；Wherein L:Cd (NO3)2·6H2The mol ratio of O is 1:1；
The structure of the double triazole cadmium complex monocrystalline of 4H thioether is [Cd (H2O)2(L)4]·7H2O；Wherein L=bis-(4-(4H-1,2,4-
Triazole-4-yl) phenyl) sulfur；
L。
The present invention further discloses the double triazole cadmium complex monocrystalline of 4H thioether and is preparing hydrogen as hydrogen storage material
Application in terms of absorption, experimental result shows: the double triazole cadmium complex monocrystalline of 4H thioether under about 3.4 MPa, 298 and 77 K
Time, the hydrogen adsorption amount of this hydrogen storage Porous materials has respectively reached 0.87 and 1.38 wt%.
The double triazole cadmium complex monocrystalline have the advantage that of a kind of 4H thioether 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 cadmium complex monocrystalline of the 4H thioether prepared by the present invention, production cost is low, and method is easy, is suitable for big
Large-scale production.The double triazole cadmium complex monocrystalline of 4H thioether has good application effect as hydrogen storage material in terms of storing hydrogen
Really.
Accompanying drawing explanation
The crystal structure figure of Fig. 1: complex monocrystal；
The accumulation graph 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 raw materials are all to buy from chemical reagents corporation both domestic and external, such as 4-
(4-aminobenzene-thio) raw material such as aniline and cadmium nitrate, through continuation purification but does not directly use.
Embodiment 1
4-(4-aminobenzene-thio) aniline: the mol ratio of double formylhydrazines is 1:4
4-(4-aminobenzene sulfur it is separately added in equipped with 50 mL three neck round bottom flasks of magneton, reflux condenser and thermometer
Base) aniline (1 mmol) and double formylhydrazine (4 mmol), start stirring 150oC, reacts 24 hours.After reaction terminates, will be anti-
Answering liquid to be down to room temperature, the precipitation obtained adds 100 mL hot methanols, after stirring and dissolving, filter, filtrate is slowly volatilized and is obtained nothing
Color solid, yield 85%；
The double formylhydrazine of 4-(4-aminobenzene-thio) aniline.
The mol ratio of the preferred 4-of the present invention (4-aminobenzene-thio) aniline and double formylhydrazine is 1:4；Reaction temperature 150 DEG C,
24 hours response time.Use " one kettle way ", 4-(4-aminobenzene-thio) aniline and double formylhydrazine are prepared in a heated condition
This organic compound.
Embodiment 2
Two (4-(4H-1,2,4-triazole-4-yl) phenyl) sulfur (L) (0.1 mmol) and Cd (NO3)2·6H2O (0.1 mmol)
In water (10 mL), stirring was filtered after half an hour, and filtrate room temperature obtains after volatilizing two weeks being suitable for the colourless of X-ray single crystal diffraction
Bulk crystals.Productivity: 40%.Elementary analysis (C16H16.5Cd0.25N6O2.25S) theoretical value (%): C, 49.40；H, 4.28；N,
21.60.Measured value: C, 49.45；H, 4.27；N, 21.64.
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 cadmium complex of 4H thioether, it is characterised in that this mono-crystalline structures uses APEX II CCD monocrystalline
Diffractometer, uses through graphite monochromatised Mok alpha ray, and λ=0.71073 is incident radiation, withω-2θScan mode is received
Collection point diffraction, obtains cell parameter through least square refinement, utilizes software to solve list from difference Fourier electron density map
Brilliant data:
Its structure is as follows:
[Cd(H2O)2(L)4]·7H2O, wherein
L=bis-(4-(4H-1,2,4-triazole-4-yl) phenyl) sulfur.
2. the preparation method of the double triazole cadmium complex monocrystalline of 4H thioether described in claim 1, it is characterised in that it is to use room temperature
Volatility process, by L and Cd (NO3)2·6H2O filters after stirring half an hour in water, and filtrate room temperature obtains after volatilizing two weeks being suitable for X-
The colourless bulk crystals of ray single crystal diffraction；Wherein L:Cd (NO3)2·6H2The mol ratio of O is 1:1；
The structure of the double triazole cadmium complex monocrystalline of 4H thioether is [Cd (H2O)2(L)4]·7H2O；Wherein L=bis-(4-(4H-1,2,
4-triazole-4-yl) phenyl) sulfur；
L。
3. the double triazole cadmium complex monocrystalline of 4H thioether described in claim 1 as hydrogen storage material in terms of preparation is to hydrogen adsorption
Application.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610602389.6A CN106317089A (en) | 2016-07-28 | 2016-07-28 | 4H thioether bis(triazol 1 yl) cadmium complex single crystal and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610602389.6A CN106317089A (en) | 2016-07-28 | 2016-07-28 | 4H thioether bis(triazol 1 yl) cadmium complex single crystal and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106317089A true CN106317089A (en) | 2017-01-11 |
Family
ID=57739287
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| CN201610602389.6A Pending CN106317089A (en) | 2016-07-28 | 2016-07-28 | 4H thioether bis(triazol 1 yl) cadmium complex single crystal and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592266A (en) * | 2015-02-26 | 2015-05-06 | 天津师范大学 | Cadmium oxyether-bis(triazolyl) nitrate complex used as potential fluorescent material and preparation method of cadmium oxyether-bis(triazolyl) nitrate complex |
| CN104610314A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Oxygen ether bitriazol cadmium chloride complex with potential fluorescent material and preparation method of complex |
| CN105669726A (en) * | 2016-01-05 | 2016-06-15 | 天津师范大学 | 4H-oxyether bistriazol cadmium complex monocrystal, and preparation method and application thereof |
-
2016
- 2016-07-28 CN CN201610602389.6A patent/CN106317089A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592266A (en) * | 2015-02-26 | 2015-05-06 | 天津师范大学 | Cadmium oxyether-bis(triazolyl) nitrate complex used as potential fluorescent material and preparation method of cadmium oxyether-bis(triazolyl) nitrate complex |
| CN104610314A (en) * | 2015-02-26 | 2015-05-13 | 天津师范大学 | Oxygen ether bitriazol cadmium chloride complex with potential fluorescent material and preparation method of complex |
| CN105669726A (en) * | 2016-01-05 | 2016-06-15 | 天津师范大学 | 4H-oxyether bistriazol cadmium complex monocrystal, and preparation method and application thereof |
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