CN106243159B - Porous cobalt-based organic-inorganic hybrid material and its preparation method and application - Google Patents
Porous cobalt-based organic-inorganic hybrid material and its preparation method and application Download PDFInfo
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- CN106243159B CN106243159B CN201610548739.5A CN201610548739A CN106243159B CN 106243159 B CN106243159 B CN 106243159B CN 201610548739 A CN201610548739 A CN 201610548739A CN 106243159 B CN106243159 B CN 106243159B
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 41
- 239000010941 cobalt Substances 0.000 title claims abstract description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003860 storage Methods 0.000 claims abstract description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-M benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 238000000921 elemental analysis Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- PAEZRCINULFAGO-OAQYLSRUSA-N (R)-homocamptothecin Chemical compound CC[C@@]1(O)CC(=O)OCC(C2=O)=C1C=C1N2CC2=CC3=CC=CC=C3N=C21 PAEZRCINULFAGO-OAQYLSRUSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000011232 storage material Substances 0.000 claims description 4
- 150000003852 triazoles Chemical group 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- 238000009396 hybridization Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000001413 cellular effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 210000003850 cellular structure Anatomy 0.000 claims 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 10
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000003446 ligand Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- -1 triazole pyrazoles Chemical class 0.000 description 1
Classifications
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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 Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a kind of porous cobalt-based organic-inorganic hybrid materials and its preparation method and application.The porous cobalt-based organic-inorganic hybrid material has following chemical formula: [Co2(HCOO)2(CPT)2](NMF)5(H2O)2, wherein CPT is 4- (1,2,4- triazol radical) benzoic acid anion, NMF is N-methyl formamide, and the organic-inorganic hybrid material is crystallized in trigonal system (trigonal), space group R-3c,Porous cobalt-based organic-inorganic hybrid material provided by the invention is at 273K~298K to C2H2Adsorbance can reach 136~178cm3g‑1, adsorption enthalpy is up to 32.6kJ/mol, has good potential using value in the storage art of acetylene, and its preparation process is simple, and synthesis material is cheap and easy to get, mild condition, is easy to be prepared on a large scale.
Description
Technical field
The present invention relates to the preparation of crystalline state organic-inorganic hybrid material, in particular to a kind of porous cobalt-based organic inorganic hybridization
Material and its preparation method and application.
Background technique
Acetylene is a kind of very important raw material of industry, is widely used in the production process of industrial polymer.
However, if safe and efficient storing acetylene is still the pendent problem of scientific circles.Main cause be acetylene high pressure with
It easily explodes under room temperature, mostly uses at present and mix during storage with acetone steam or filled out in the container of storage
Fill porous material.This reduces the purity of acetylene gas and the cost for increasing its storage.In nearest twenties years,
Porous organic-inorganic hybrid material shows wide application prospect in the storage art of gas, aperture is adjustable, function can
Modification, property predictability the features such as impart many other polyporous materials of organic-inorganic hybrid material cannot compare it is excellent
Point.People can be shown and gas minute by introducing metallic voids point or polar organic atoms or functional group come reinforcing material
The active force of son, to realize the purpose for increasing storage capacity.In addition, ligand field-effect can also generate phase interaction to gas molecule
With, such as the stronger phase interaction of acetylene molecule generation with π acidity of the biggish azacyclo- meeting selectivity of the Pka such as triazole pyrazoles
With.In general, what porous organic-inorganic hybrid material was made of inorganic node and organic ligand, it is compared to inorganic metal
Cluster node, organic ligand have stronger designability.Then still rarely have at present about the more of energy selectivity efficient storage acetylene
The report of hole organic-inorganic hybrid material.
Summary of the invention
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of porous cobalt-based organic inorganic hybridization materials
Material and its preparation method and application.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of porous cobalt-based organic-inorganic hybrid materials, it has following chemical formula: [Co2
(HCOO)2(CPT)2](NMF)5(H2O)2, wherein CPT is 4- (1,2,4- triazol radical) benzoic acid anion, NMF is N-methyl
The skeleton symbol of formamide, CPT is as follows:
The porous cobalt-based organic-inorganic hybrid material is crystallized in trigonal system (trigonal), space group R-3c,
Further, the elemental analysis result of the porous cobalt-based organic-inorganic hybrid material are as follows: C 39.57, H 4.65,
N 16.74。
Further, the porous cobalt-based organic-inorganic hybrid material has is connected by triazole group, carboxyl and formate
Meet one-dimensional S type secondary construction unit (SBUs) chain of metallic cobalt formation, the Co in the cellular chain2+It is all hexa-coordinate, and respectively
The octahedra caged knot of deformation is formed with the oxygen atom ligand on the nitrogen-atoms of triazole, the oxygen atom of carboxylic acid and formate
Structure, the octahedron cage structure accumulate to form hexagonal one-dimensional tunnel structure in the direction crystal a.
Further, the porosity of the porous cobalt-based organic-inorganic hybrid material is 48.6%~53.8%.
The embodiment of the invention also provides the methods for preparing the porous cobalt-based organic-inorganic hybrid material, comprising: will rub
You are than being that cobalt salt, the HCPT organic ligand of 3:1~5:1 are sufficiently mixed in a solvent, later under the conditions of temperature is 80~90 DEG C
48~72h of curing process obtains red bulk crystals, the as porous cobalt-based organic-inorganic hybrid material；
Wherein, the cobalt salt includes cobalt nitrate hexahydrate, and the solvent includes NMF and H2O。
Further, the preparation method includes: to be uniformly mixed cobalt salt with HCPT ligand to obtain mixture, is then added
Into solvent, 30~40min of stirring at normal temperature.
It is more preferred, the mixture with NMF, H2The amount ratio of O is 55mg:3mL:1mL~55mg:5mL:1mL.
In some more specific case study on implementation, the preparation method includes: to add cobalt nitrate hexahydrate, HCPT ligand
Enter into NMF and water, stirring at normal temperature 30min obtains mixed liquor；72h is baked at 80 DEG C, then separates solid；It will be upper with NMF
It states solid to wash 3~5 times, red blocky hydridization crystalline material can be obtained.
The embodiment of the invention also provides the porous cobalt-based organic-inorganic hybrid materials in C2H2The application of storage art.
The embodiment of the invention also provides a kind of C2H2Storage material or selective absorbent, by the porous cobalt-based
Organic-inorganic hybrid material is made.
The embodiment of the invention also provides a kind of C2H2The preparation method of storage material or selective absorbent, comprising: will
The porous cobalt-based organic-inorganic hybrid material impregnates 60~72h with methylene chloride, the vacuum for being later 30~40 DEG C in temperature
24~36h of lower heating.
In some more specific case study on implementation, a kind of C2H2The preparation method of selective absorbent include: by institute
It states porous cobalt-based organic-inorganic hybrid material methylene chloride and impregnates 72 hours to exchange the high boiling NMF in its duct points
Son takes and heats the hybrid material after exchange for 24 hours to remove the dichloro molecule in duct at 30 DEG C, under vacuum degree 1m bar,
It is filled into storage C2H2It is spare in the device of adsorbent.
Compared with prior art, the invention has the advantages that
(1) the porous cobalt-based organic-inorganic hybrid material provided is at 273K and 298K to C2H2Adsorbance can reach 178
And 136cm3g-1, adsorption enthalpy is up to 32.6kJ/mol, therefore has good potential using value in the storage art of acetylene；
(2) the porous cobalt-based organic-inorganic hybrid material preparation process provided is simple, and synthesis material is cheap and easy to get, condition temperature
Be easy to be prepared on a large scale.
Detailed description of the invention
Fig. 1 is that embodiment 1 obtains [Co2(HCOO)2(CPT)2](NMF)5(H2O)2Single crystal diffraction structure chart；
Fig. 2 is that embodiment 1 obtains [Co2(HCOO)2(CPT)2](NMF)5(H2O)2Double-pore structure schematic diagram；
Fig. 3 is that embodiment 1 obtains [Co2(HCOO)2(CPT)2](NMF)5(H2O)2BET test chart；
Fig. 4 is that embodiment 1 obtains [Co2(HCOO)2(CPT)2](NMF)5(H2O)2Acetylene adsorption curve figure；
Fig. 5 is that embodiment 1 obtains [Co2(HCOO)2(CPT)2](NMF)5(H2O)2Adsorption enthalpy calculated result figure.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution relates generally to a kind of porous cobalt-based organic-inorganic hybrid material constructed based on triazolylcarboxylic acid's ligand and its preparation
Methods and applications, the porous cobalt-based organic-inorganic hybrid material show biggish specific surface area and porosity, especially gas
Absorption test result shows the material at room temperature to C2H2Adsorbance with higher and affinity, can be applied to second
The storage art of alkynes gas.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated, the method in the following example, is the conventional method of this field unless otherwise instructed.
Embodiment 1: the preparation of porous cobalt-based organic-inorganic hybrid material
Mixture is obtained by being uniformly mixed in 45mg cobalt nitrate hexahydrate, 15mgHCPT ligand beaker, 3mLNMF is then added
With 1mL water, stirring at normal temperature 30min obtains mixed liquor；Above-mentioned mixed liquor is transferred to bottle of the 10mL with screw stopper 80
48h is baked at DEG C, obtains product after being cooled to room temperature filtering, separation；Above-mentioned solid is washed 3 times with NMF, red can be obtained
Strip hybrid material crystal, calculating yield based on organic ligand is 66%.Elemental analysis result: C 39.57, H 4.65, N
16.74。
Embodiment 2: the preparation of porous cobalt-based organic-inorganic hybrid material
Mixture is obtained by being uniformly mixed in 60mg cobalt nitrate hexahydrate, 15mgHCPT ligand beaker, 4mLNMF is then added
With 1mL water, stirring at normal temperature 30min obtains mixed liquor；Above-mentioned mixed liquor is transferred to bottle of the 10mL with screw stopper 90
72h is baked at DEG C, obtains product after being cooled to room temperature filtering, separation；Above-mentioned solid is washed 3 times with NMF, red can be obtained
Strip hybrid material crystal, calculating yield based on organic ligand is 59%.Elemental analysis result: C 39.57, H 4.65, N
16.74。
Embodiment 3: the preparation of porous cobalt-based organic-inorganic hybrid material
Mixture is obtained by being uniformly mixed in 50mg cobalt nitrate hexahydrate, 15mgHCPT ligand beaker, is then added
3.5mLNMF and 1mL water, stirring at normal temperature 30min obtain mixed liquor；Above-mentioned mixed liquor is transferred to 10mL with screw stopper
Bottle bakes 60h at 85 DEG C, obtains product after being cooled to room temperature filtering, separation；Above-mentioned solid is washed 3 times with NMF
Red bar hybrid material crystal is obtained, calculating yield based on organic ligand is 62%.Elemental analysis result: C 39.57, H
4.65,N 16.74。
Institute's cobalt-based organic-inorganic hybrid material further characterizes in Example 1, and process is as follows:
(1) crystal structure determination
Under petrographic microscope, the monocrystalline for choosing suitable size carries out X-ray single crystal diffraction experiment at room temperature.Using
Supernova type X-ray single crystal diffractometer, using by graphite monochromatised Mo-KαRayPhenol is incidence
Radiation source, withScanning mode collects point diffraction, cell parameter is obtained by least square refinement, from difference fourier
Electron-density map solves crystal structure using SHELXL-97 direct method, and corrects through lorent and polarity effect.All H are former
Son is synthesized by difference Fourier and is calculated by ideal position and determined, detailed axonometry data are shown in Table 1.Detailed axonometry
Data are shown in Table 1, and important bond distance and bond angle data are shown in Table 2 and table 3, and crystal structure is shown in Fig. 1.
1 cobalt-based organic-inorganic hybrid material of table
a R1=Σ | | Fo|–|Fc||/Σ|Fo|.b wR2=| Σ w (| Fo|2–|Fc|2)|/Σ|w(Fo)2|1/2,where w
=1/ [σ2(Fo 2)+(aP)2+ bP] .P=(Fo 2+2Fc 2)/3。
The main bond distance of 2 cobalt-based organic-inorganic hybrid material of table*
Main bond angle [°] * of 3 cobalt-based organic-inorganic hybrid material of table
Symmetry operation code: 14/3-X, 2/3-X+Y, 1/6-Z；21/3+Y, 2/3-X+Y, 2/3-Z；35/3-X,4/3-Y,1/
3-Z；44/3-Y, 2/3+X-Y, -1/3+Z；51/3-Y+X, -1/3+X, 2/3-Z；62/3+Y-X, 4/3-X, 1/3+Z；71/3-Y+
X,2/3-Y,1/6-Z；8+Y,+X,1/2-Z.
(2) gas absorption is tested: gas absorption desorption curve will be made by measuring on Mike's 3Flex gas test work station
The sample got ready is de-gassed first on instrument, and temperature condition is 30 DEG C, and the processing time is 12h, and deaerate laggard promoting the circulation of qi
The analysis of body adsorption/desorption, process Automatic Control.
Fig. 3 is [Co2(HCOO)2(CPT)2](NMF)5(H2O)2BET phenogram, test temperature 77K, test result table
The bright compound is microcellular structure, and shows IV type adsorption isotherm, and higher-pressure region shows mesoporous hysteresis loop, explanation
There is crystal defects.
Fig. 4 is [Co2(HCOO)2(CPT)2](NMF)5(H2O)2Gas absorption curve graph, test 273 and 298K respectively
Under C2H2, show in figure: the product is in 273K and 298K to C2H2Adsorbance can reach 178 and 144cm3/ g, adsorption enthalpy
Up to 32.6kJ/mol illustrates that the hybrid material has to C2H2Storage capacity and affinity with higher.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of porous cobalt-based organic-inorganic hybrid material, it is characterised in that it has following chemical formula: [Co2(HCOO)2
(CPT)2](NMF)5(H2O)2, wherein CPT is 4- (1,2,4- triazol radical) benzoic acid anion, NMF is N-methyl formamide,
The skeleton symbol of CPT is as follows:
The porous cobalt-based organic-inorganic hybrid material is crystallized in trigonal system (trigonal), space group R-3c,The porous cobalt-based organic inorganic hybridization material
Expect that there is the one-dimensional S type secondary formed by triazole group, carboxyl and formate connection metallic cobalt to construct cellular chain, the unit
Co in chain2+Be hexa-coordinate, and respectively with the nitrogen-atoms of triazole, carboxylic acid oxygen atom and formate on oxygen atom match
Position formed deformation octahedra cage structure, it is described octahedron cage structure the direction crystal a accumulate to be formed it is hexagonal one-dimensional
Cellular structure；And the porosity of the porous cobalt-based organic-inorganic hybrid material is 48.6%~53.8%；The porous cobalt
The elemental analysis result of base organic-inorganic hybrid material are as follows: C 39.57, H 4.65, N 16.74.
2. the preparation method of porous cobalt-based organic-inorganic hybrid material as described in claim 1, characterized by comprising: general mole
It is uniformly mixed than cobalt salt, the HCPT organic ligand for 3:1~5:1 and obtains mixture, be then added in solvent, stirring at normal temperature 30
~40min, later 48~72h of curing process under the conditions of temperature is 80~90 DEG C, obtain red bulk crystals, as described
Porous cobalt-based organic-inorganic hybrid material；
Wherein, the cobalt salt is cobalt nitrate hexahydrate, and the solvent is NMF and H2O, the mixture and NMF, H2The amount ratio of O is
55mg:3mL:1mL~55mg:5mL:1mL.
3. porous cobalt-based organic-inorganic hybrid material as described in claim 1 is in C2H2The application of storage art.
4. a kind of C2H2Storage material or selective absorbent, the porous cobalt-based organic-inorganic hybrid material as described in claim 1
It is made.
5. a kind of C2H2The preparation method of storage material or selective absorbent, characterized by comprising: by claim 1 institute
The porous cobalt-based organic-inorganic hybrid material stated impregnates 60~72h with methylene chloride, the condition for being later 30~40 DEG C in temperature
24~36h of lower heating in vacuum.
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|---|---|---|---|---|
| CN103665006A (en) * | 2013-12-13 | 2014-03-26 | 南开大学 | Porous metal-organic framework hybrid material as well as preparation method and application thereof |
| CN104628789A (en) * | 2015-01-26 | 2015-05-20 | 郑州轻工业学院 | Microporous cobalt coordination polymer with broad-spectrum gas adsorption property and preparation method thereof |
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| CN103665006A (en) * | 2013-12-13 | 2014-03-26 | 南开大学 | Porous metal-organic framework hybrid material as well as preparation method and application thereof |
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