CN105294705A - Porphyrin-based metal organic framework material with ultrahigh stability and synthetic method - Google Patents
Porphyrin-based metal organic framework material with ultrahigh stability and synthetic method Download PDFInfo
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- CN105294705A CN105294705A CN201510669999.3A CN201510669999A CN105294705A CN 105294705 A CN105294705 A CN 105294705A CN 201510669999 A CN201510669999 A CN 201510669999A CN 105294705 A CN105294705 A CN 105294705A
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Abstract
The invention discloses a porphyrin-based metal organic framework material with ultrahigh stability and a synthetic method, and belongs to the technical field of crystalline state materials. The chemical formula of the porphyrin-based metal organic framework material is [Ni9.77C56.64N21.24O10.92H35.47]. Under the closed condition, an organic ligand 5,10,15,20-tetra(1 hydrogen-pyrazol-4-radical) porphyrin(H4TPP) and nickel acetate generate a solvothermal reaction in N,N-dimethylformamide to obtain the porphyrin-based metal organic framework material. The metal organic framework material has ultrahigh stability, and materials of this kind can be possibly applied widely.
Description
Technical field
The invention belongs to the technical field of crystalline material, technology relates to metal-organic coordination polymer material, the synthetic method of metal-organic framework materials and the research of stability thereof of feature to be an example based on porphyrin be part.
Background technology
Porphyrins, because of its special performance, has very important application in a lot of fields, as cancer therapy drug, and catalyzer, sensitizer, pH sensor aspect.But it easily occurs autohemagglutination in the application, the shortcomings such as reunion, have had a strong impact on the research of porphyrins performance.Metal-organic framework (metal-organicframeworks, MOFs), to be constructed by coordinate bond by metal ion or metal cluster and organic ligand and form, as the porous material that a class is novel, there is tactical rule, porosity be high, specific surface area is large, the feature such as structure function easy-regulating, gas adsorption be separated, catalysis, fluorescence, the field such as electrochemistry have potential application.Porphyryl is embedded in MOFs have easily separated, can be recycled, the advantages such as reunion can not occur, the MOFs therefore constructed based on porphyrin part more and more receives people and studies widely.
The application of porphyrin relates to harsh chemical environment more, and so chemical stability just becomes the vital problem of porphyryl MOFs.Therefore, develop the porphyryl MOFs with high stability, for the application of widening these materials, there is deep meaning.Directly effective strategy is the coordinate bond intensity strengthening metal ion and organic ligand, and the secondary construction unit of the metal ion formation of high-valence state, as [Zr
6o
4(OH)
4(CO
2)
12] and [M
3o
x(CO
2)
6] (M=Al
3+, Cr
3+, Fe
3+; X=OH
-, F
-, Cl
-) and carboxylic acid compound just become the object that people extensively study.Utilize this method, several in acidic solution and neutral aqueous solution the porphyryl MOFs of high stable be developed, as PCN-222 and PCN-600, the obvious shortcoming that these materials exist easily is decomposed in alkaline solution.In recent years, report a class in document and in basic solution, maintain fabulous stability based on many nitrogen azole MOFs.
The present invention reports the synthetic method that an example has the porphyrin pyrazoles MOFs of ultrastability.
Summary of the invention
The object of the present invention is to provide the synthetic method of the porphyryl metal-organic framework of a routine ultrastability.
The metal-organic framework materials of a kind of three-dimensional porphyryl of the present invention, is characterized in that, be the metal-organic framework materials be made up of metallic nickel and porphyrin part, chemical molecular formula is [Ni
9.77c
56.64n
21.24o
10.92h
35.47], its mesoporphyrin part 5,10,15,20-tetra-(1 hydrogen-pyrazoles-4-base) porphyrin (H
4tPP) structural formula is as follows:
Connect the angle of constructing from skeleton, the crystalline structure of this 3-dimensional metal organic framework material belongs to isometric system, and spacer is Pm-3m, and unit cell parameters is:
α=β=γ=90 °.
This metal-organic framework comprises the secondary construction unit (SBU) by eight core Ni: Ni
8o
6n
24.Wherein eight nickle atoms connect 6 μ
4-O defines a Ni
8o
6core, has finally constructed a desirable Ni
8cubes, this cubical summit is occupied by nickle atom, and each by a μ
4-O is connected with the nickel on its four summits respectively, and six faces are by 6 μ
4-O covers; Ni
8on each limit cubical, two Ni are connected by from the pyrazoles in porphyrin, finally obtain [Ni
8o
6(N
2)
12]
12+secondary construction unit.
Each SBU is by tetradentate ligands (TPP
4-) be connected with 12 SBUs of surrounding.In this metal-organic framework, there is a kind of SBU and tetradentate ligands (TPP
4-) the cubical cage structure (can see Fig. 4) that forms, its length of side is about
these cubes cage structures are by sharing TPP
4-the limit of part is connected thus constitutes three-dimensional skeleton structure.
From topology angle, if by the SBU of eight core nickel, [Ni
8o
6(N
2)
12] be simplified to 12 nodes connected, by tetradentate ligands TPP
4-be simplified to the node of four connections, so whole skeleton can be simplified to 4, and 12 nets connected, its Shi Laifuli symbol is (4
366
30) (4
46
2)
3, belong to the topology of ftw type.The specific surface area that under 77K, nitrogen adsorption curve is calculated is 1339m
2g
-1, prove that this material is under different acid-base condition by PXRD and nitrogen adsorption characterization method, particularly after 100 DEG C of saturated sodium hydroxide boil 24h, still keep good degree of crystallinity and porosity.
The synthetic method of metal-organic framework materials of the present invention, comprises the following steps:
Under air-proof condition, organic ligand H
4tPP (5,10,15,20-tetra-(1 hydrogen-pyrazoles-4-base) porphyrin) and four hydration nickel acetates (Ni (OAc)
24H
2o) in the mixing solutions of DMF (DMF), water and triethylamine, the crystal of this metal-organic framework is obtained via solvent thermal reaction.
Wherein organic ligand H
4tPP (5,10,15,20-tetra-(1 hydrogen-pyrazoles-4-base) porphyrin) be 1:(1 ~ 5 with the mol ratio of four hydration nickel acetates), the N of the corresponding 0.5mL ~ 4mL of four hydration nickel acetates of every 0.05 mmole, dinethylformamide, the triethylamine of 0.2mL ~ 2mL, 0.005 ~ 0.05mL water; The temperature of described thermal response is 60 DEG C-120 DEG C, and the reaction times is 40-100 hour.
This metal-organic framework has ultrastability, the chemical stability particularly in alkaline solution, is that known first case can at 100 DEG C, the MOF of stable existence in saturated sodium hydroxide solution, and complete maintenance degree of crystallinity and porosity.
The advantages such as the well-regulated cage structure of metal-organic framework tool of the present invention, skeleton are stable, chemical stability is strong, make the widespread use of porphyryl MOFs in basic solution become possibility.Preparation method's technique of the present invention is simple, easy to implement, productive rate is high, is conducive to large-scale popularization.
Accompanying drawing explanation
Fig. 1 is that the simulation (theory) of this metal-organic framework is schemed with test PXRD.
Fig. 2 is the secondary construction unit figure of this metal-organic framework.
Fig. 3 is the connection mode figure of this metal-organic framework.
Fig. 4 is the three-dimensional structure schematic diagram of this metal-organic framework.
Fig. 5 is that the stability study PXRD of this metal-organic framework materials schemes.
Fig. 6 is this metal-organic framework 77K nitrogen adsorption isotherm figure at different conditions.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
By organic ligand H
4tPP (0.035 mmole) mixes in the DMF of 1mL with S tetra-hydration nickel acetate (0.035 mmole), adds 0.05mL triethylamine and 0.05mL water, encloses in bottle.Within 48 hours, obtain the crystal of this metal-organic framework via thermal response at 100 DEG C.
Embodiment 2
By organic ligand H
4tPP (0.035 mmole) mixes in the DMF of 1.5mL with four hydration nickel acetates (0.035 mmole), adds 0.05mL triethylamine and 0.05mL water, encloses in bottle.Within 48 hours, obtain the crystal of this metal-organic framework via thermal response at 100 DEG C.
Embodiment 3
By organic ligand H
4tPP (0.035 mmole) mixes in the DMF of 2.0mL with four hydration nickel acetates (0.035 mmole), adds 0.05mL triethylamine and 0.05mL water, encloses in bottle.Within 48 hours, obtain the crystal of this metal-organic framework via thermal response at 100 DEG C.
Embodiment 4
By organic ligand H
4tPP (0.035 mmole) mixes in the DMF of 2.0mL with four hydration nickel acetates (0.035 mmole), adds 0.1mL triethylamine and 0.05mL water, encloses in bottle.Within 48 hours, obtain the crystal of this metal-organic framework via thermal response at 100 DEG C.
The test result of the product of above-described embodiment gained is identical, specifically sees following:
(1) determination of crystalline structure:
Choose sizeable powder, under 298K, utilize PANalyticalX ' PertPRO high resolution powder diffractometer to collect data.Data gathering use through graphite monochromator monochromatization Cu-K α (
) target ray.Carry out structural simulation by MaterialStudio6.0 software, then with TOPAS software, refine has been carried out to crystalline structure.Crystallographic data is in table 1.
The crystallographic data of table 1 metal-organic framework materials
The structure iron of Fig. 1 shows: this metal-organic framework comprises the secondary construction unit (SBU) by eight core Ni: Ni
8o
6n
24.Wherein eight nickle atoms connect 6 μ
4-O defines a Ni
8o
6core, finally constructed a desirable Ni8 cubes, this cubical summit is occupied by nickle atom, and six faces are by 6 μ
4-O covers.Ni8 each limit cubical is connected with from the pyrazoles in porphyrin and finally obtains [Ni
8o
6(N
2)
12]
12+secondary construction unit.
The structure iron of Fig. 2 shows: in this metal-organic framework, and each SBU is by tetradentate ligands (TPP
4-) be connected with 12 SBUs of surrounding.Belong to 12 and connect nickel metal-organic framework.
The structure iron of Fig. 3 shows: in this metal-organic framework, there is a kind of cubical cage structure.Its length of side is about
the mode that these cage structures are connected is all by shared TPP
4-the limit of part.
(2) sign of ultrastability
The stability of metal-organic framework materials is measured by PXRD; Operation steps: soak 24h under soaking 24h, 0.1mMHCl room temperature under respectively this material of 10mg being immersed in 0.01mMHCl room temperature, in 1M sodium hydroxide solution, soak 24h at 100 DEG C, soak in 10M sodium hydroxide solution at 100 DEG C soak 24h in 24h and 100 DEG C of saturated sodium hydroxide solution after measure.
Metal-organic framework materials 77K nitrogen adsorption under different acid-base condition characterizes the feature of its porosity; Operation steps is: get the novel material after 60mg activation respectively, be immersed in 0.1M hydrochloric acid 24h under room temperature, soak 24h in saturated sodium hydroxide solution at 100 DEG C after the nitrogen adsorption done characterize.
Fig. 4 is the PXRD figure that invention material is tested under different chemical condition, can find out that this material all keeps satisfactory stability and degree of crystallinity in acid solution, alkaline solution.
Fig. 5 is the new synthetic sample of material of the present invention, soak 24h and 100 DEG C, saturated sodium hydroxide under 0.1mMHCl room temperature at soak the 77K nitrogen adsorption isotherm after 24h.As can be seen from the figure, this material all keeps complete porosity in different acid-base solutions, the N that this material is maximum
2adsorptive capacity is 520cm
3/ g, the specific surface area calculated with it (BET) is 1339m
2/ g.
Claims (7)
1. a metal-organic framework materials for three-dimensional porphyryl, is characterized in that, be the metal-organic framework materials be made up of metallic nickel and porphyrin part, chemical molecular formula is [Ni
9.77c
56.64n
21.24o
10.92h
35.47], its mesoporphyrin part 5,10,15,20-tetra-(1 hydrogen-pyrazoles-4-base) porphyrin (H
4tPP) structural formula is as follows:
2. according to the metal-organic framework materials of a kind of three-dimensional porphyryl of claim 1, it is characterized in that, connect the angle of constructing from skeleton, the crystalline structure of this 3-dimensional metal organic framework material belongs to isometric system, and spacer is Pm-3m, and unit cell parameters is:
α=β=γ=90 °.
3. according to the metal-organic framework materials of a kind of three-dimensional porphyryl of claim 1, it is characterized in that, this metal-organic framework comprises the secondary construction unit (SBU) by eight core Ni: Ni
8o
6n
24, wherein eight nickle atoms connect 6 μ
4-O defines a Ni
8o
6core, has finally constructed a desirable Ni
8cubes, this cubical summit is occupied by nickle atom, and each by a μ
4-O is connected with the nickel on its four summits respectively, and six faces are by 6 μ
4-O covers; Ni
8on each limit cubical, two Ni are connected by from the pyrazoles in porphyrin, finally obtain [Ni
8o
6(N
2)
12]
12+secondary construction unit.
4. according to the metal-organic framework materials of a kind of three-dimensional porphyryl of claim 3, it is characterized in that, each SBU is by tetradentate ligands (TPP
4-) be connected with 12 SBUs of surrounding; In this metal-organic framework, there is a kind of SBU and tetradentate ligands (TPP
4-) the cubical cage structure that forms, its length of side is
these cubes cage structures are by sharing TPP
4-the limit of part is connected thus constitutes three-dimensional skeleton structure.
5. according to the metal-organic framework materials of a kind of three-dimensional porphyryl of claim 1, it is characterized in that, from topology angle, if by the SBU of eight core nickel, [Ni
8o
6(N
2)
12] be simplified to 12 nodes connected, by tetradentate ligands TPP
4-be simplified to the node of four connections, so whole skeleton can be simplified to 4, and 12 nets connected, its Shi Laifuli symbol is (4
366
30) (4
46
2)
3, belong to the topology of ftw type.
6. prepare the method for the metal-organic framework materials of a kind of three-dimensional porphyryl of claim 1, it is characterized in that, comprise the following steps: under air-proof condition, organic ligand H
4tPP (5,10,15,20-tetra-(1 hydrogen-pyrazoles-4-base) porphyrin) and four hydration nickel acetates (Ni (OAc)
24H
2o) in the mixing solutions of DMF (DMF), water and triethylamine, the crystal of this metal-organic framework is obtained via solvent thermal reaction.
7. according to the method for claim 6, it is characterized in that, organic ligand H
4tPP (5,10,15,20-tetra-(1 hydrogen-pyrazoles-4-base) porphyrin) be 1:(1 ~ 5 with the mol ratio of four hydration nickel acetates), the N of the corresponding 0.5mL ~ 4mL of four hydration nickel acetates of every 0.05 mmole, dinethylformamide, the triethylamine of 0.2mL ~ 2mL, 0.005 ~ 0.05mL water; The temperature of described thermal response is 60 DEG C-120 DEG C, and the reaction times is 40-100 hour.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106905538A (en) * | 2017-02-24 | 2017-06-30 | 浙江省农业科学院 | A kind of zinc-containing metal organic framework materials and its preparation method and application |
| CN106905537A (en) * | 2017-02-23 | 2017-06-30 | 浙江省农业科学院 | The synthetic method of the metal-organic framework material with fluorescence property and its application |
| CN106927535A (en) * | 2017-03-16 | 2017-07-07 | 南京师范大学 | Method based on the photocatalytic degradation phenolic comp ' ds pollution for stablizing porphyrin metal organic framework material |
| CN109999915A (en) * | 2019-04-28 | 2019-07-12 | 大连民族大学 | One kind being used for CO2The porphyryl metal-organic framework materials and preparation method thereof of cyclisation catalysis reaction |
| CN112210084A (en) * | 2020-10-27 | 2021-01-12 | 洪月恒 | Preparation method of metal organic framework with photocatalytic reduction of carbon dioxide |
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| CN106905537A (en) * | 2017-02-23 | 2017-06-30 | 浙江省农业科学院 | The synthetic method of the metal-organic framework material with fluorescence property and its application |
| CN106905537B (en) * | 2017-02-23 | 2019-11-08 | 浙江省农业科学院 | The synthetic method and its application of metal-organic framework materials with fluorescence property |
| CN106905538A (en) * | 2017-02-24 | 2017-06-30 | 浙江省农业科学院 | A kind of zinc-containing metal organic framework materials and its preparation method and application |
| CN106905538B (en) * | 2017-02-24 | 2019-11-08 | 浙江省农业科学院 | A kind of zinc-containing metal organic framework materials and its preparation method and application |
| CN106927535A (en) * | 2017-03-16 | 2017-07-07 | 南京师范大学 | Method based on the photocatalytic degradation phenolic comp ' ds pollution for stablizing porphyrin metal organic framework material |
| CN106927535B (en) * | 2017-03-16 | 2020-06-05 | 南京师范大学 | Method for photocatalytic degradation of phenolic pollutants based on stable porphyrin metal organic framework material |
| CN109999915A (en) * | 2019-04-28 | 2019-07-12 | 大连民族大学 | One kind being used for CO2The porphyryl metal-organic framework materials and preparation method thereof of cyclisation catalysis reaction |
| CN109999915B (en) * | 2019-04-28 | 2021-12-21 | 大连民族大学 | For CO2Porphyrin-based metal organic framework material for cyclization catalytic reaction and preparation method thereof |
| CN112210084A (en) * | 2020-10-27 | 2021-01-12 | 洪月恒 | Preparation method of metal organic framework with photocatalytic reduction of carbon dioxide |
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