CN105294705B - The porphyryl metal-organic framework materials and synthetic method of a kind of ultrastability - Google Patents
The porphyryl metal-organic framework materials and synthetic method of a kind of ultrastability Download PDFInfo
- Publication number
- CN105294705B CN105294705B CN201510669999.3A CN201510669999A CN105294705B CN 105294705 B CN105294705 B CN 105294705B CN 201510669999 A CN201510669999 A CN 201510669999A CN 105294705 B CN105294705 B CN 105294705B
- Authority
- CN
- China
- Prior art keywords
- metal
- organic framework
- tpp
- porphyrin
- porphyryl
- 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.)
- Expired - Fee Related
Links
- 0 C*(C1)*=CC1C(C1=CC=C2*1C)=C(C=C1)*=C1C(C1=C*(C)*=C1)=C(*1C)C=CC1=C(C1=C*(C)*=C1)C(C=C1)=*C1=C2C1=C*(C)*=C1 Chemical compound C*(C1)*=CC1C(C1=CC=C2*1C)=C(C=C1)*=C1C(C1=C*(C)*=C1)=C(*1C)C=CC1=C(C1=C*(C)*=C1)C(C=C1)=*C1=C2C1=C*(C)*=C1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The porphyryl metal-organic framework materials and synthetic method of a kind of ultrastability, belong to the technical field of crystalline material.Chemical molecular formula is [Ni9.77C56.64N21.24O10.92H35.47].Under sealing condition, organic ligand 5,10,15,20 four (base of 1 hydrogen pyrazoles 4) porphyrin (H4TPP porphyryl metal-organic framework materials) are obtained via solvent thermal reaction in N, N dimethylformamides with four hydration nickel acetates；This metal-organic framework materials shows the stability of superelevation, and possibility is provided for the extensive use of such material.
Description
Technical field
The invention belongs to the technical field of crystalline material, technology is related to metal-organic coordination polymer material, is characterized in one
Research of the example based on porphyrin for the synthetic method and its stability of the metal-organic framework materials of part.
Background technology
Porphyrins has very important application, such as cancer therapy drug in many fields, urged because of its special performance
Agent, emulsion, pH sensors etc..But it the shortcomings of autohemagglutination, reunion easily occurs in the application, porphyrin has been had a strong impact on
The research of class compounds property.Metal-organic framework (metal-organic frameworks, MOFs), by metal ion or
Metal cluster is constructed by coordinate bond with organic ligand and formed, and as a kind of new porous material, has tactical rule, porosity
The features such as high, big, the structure function easy-regulating of specific surface area, in gas absorption and separate, be catalyzed, the field tool such as fluorescence, electrochemistry
There is potential application.Porphyryl is embedded in MOFs have the advantages that it is easily separated, can be recycled, will not reunite, therefore
People are more and more received based on the MOFs that porphyrin part is constructed widely to study.
The application of porphyrin is related to harsh chemical environment more, then chemical stability just becomes porphyryl MOFs to pass
The problem of important.Therefore, the porphyryl MOFs with high stability is developed for widening the applications of these materials with deeply
Meaning.A kind of directly effective strategy is the coordination bond strength for strengthening metal ion and organic ligand, the metal ion of high-valence state
The secondary construction unit of composition, such as [Zr6O4(OH)4(CO2)12] and [M3OX(CO2)6] (M=Al3+,Cr3+,Fe3+；X=OH-,F-,
Cl-) and carboxylic acid compound just become the widely studied object of people.Using this method, it is several acid solution and in
The porphyryl MOFs of high stable is developed in the property aqueous solution, such as PCN-222 and PCN-600, one existing for these materials
The shortcomings that obvious, is easily decomposed in aqueous slkali.In recent years, one kind is reported in document based on more nitrogen azole MOFs to exist
Fabulous stability is maintained in alkaline solution.
The present invention reports a synthetic method with the porphyrin pyrazoles MOFs of ultrastability.
The content of the invention
It is an object of the invention to provide the synthetic method of the porphyryl metal-organic framework of a ultrastability.
The metal-organic framework materials of a kind of three-dimensional porphyryl of the present invention, it is characterised in that be by metallic nickel and porphyrin
The metal-organic framework materials that part is formed, chemical molecular formula is [Ni9.77C56.64N21.24O10.92H35.47], its mesoporphyrin part
5,10,15,20- tetra- (1 hydrogen-pyrazoles -4- bases) porphyrin (H4TPP structural formula) is as follows：
The angle constructed from skeleton connection, the crystal structure of the 3-dimensional metal organic framework material belongs to cubic system, empty
Between group be Pm-3m, cell parameter is：α=β=γ=90 °.
The metal-organic framework includes the secondary construction unit (SBU) by eight core Ni：Ni8O6N24.Wherein eight nickle atoms
Connect 6 μ4- O forms a Ni8O6Core, a preferable Ni is finally constructed8Cube, this cubical summit by
Nickle atom occupies, and each face is by a μ4Nickel of-the O respectively with its four summits is connected, and six faces are by 6 μ4- O is covered；Ni8It is vertical
Two Ni are connected by the pyrazoles in porphyrin on each side of cube, have finally given [Ni8O6(N2)12]12+Secondary is constructed
Unit.
Each SBU passes through tetradentate ligandses (TPP4-) be connected with 12 SBUs of surrounding.In the metal-organic framework,
A kind of SBU and tetradentate ligandses (TPP be present4-) the cubical cage structure (reference can be made to Fig. 4) that forms, its length of side is aboutThese cube cage structures are by sharing TPP4-The side of part is connected so as to constitute the skeleton structure of three-dimensional.
In terms of topology angle, if SBU, [Ni by eight core nickel8O6(N2)12] node of 12 connections is simplified to, by four
Tooth part TPP4-It is simplified to the node of four connections, then whole skeleton can be simplified to the net of 4,12 connections, its Shi Laifulifu
Number be (436·630)(44·62)3, belong to the topologys of ftw types.The counted specific surface area of nitrogen adsorption curve is under 77K
1339m2g-1, the material is proved under different acid-base conditions by PXRD and nitrogen adsorption characterization method, particularly at 100 DEG C
Saturation sodium hydroxide still keeps good crystallinity and porosity after boiling 24h.
The synthetic method of metal-organic framework materials of the present invention, comprises the following steps：
Under air-proof condition, organic ligand H4TPP (5,10,15,20- tetra- (1 hydrogen-pyrazoles -4- bases) porphyrin) and four hydration vinegar
Sour nickel (Ni (OAc)2·4H2O) in the mixed solution of DMF (DMF), water and triethylamine, via solvent heat
Reaction obtains the crystal of the metal-organic framework.
Wherein organic ligand H4TPP (5,10,15,20- tetra- (1 hydrogen-pyrazoles -4- bases) porphyrin) rubs with four hydration nickel acetates
You are than being 1:(1~5), every 0.05 mM of four hydration nickel acetates correspond to 0.5mL~4mL DMF,
0.2mL~2mL triethylamine, 0.005~0.05mL water；The temperature of the thermal response is 60 DEG C -120 DEG C, reaction time 40-
100 hours.
This metal-organic framework has ultrastability, the chemical stability particularly in aqueous slkali, is known
One can be at 100 DEG C, the MOF that is stabilized in saturation sodium hydroxide solution, and completely keep crystallinity and porosity.
The metal-organic framework of the present invention has the advantages that well-regulated cage structure, skeleton are stable, chemical stability is strong,
So that extensive uses of the porphyryl MOFs in alkaline solution becomes possible to.Preparation method technique of the present invention is simple, it is easy to implement,
Yield is high, is advantageous to promote on a large scale.
Brief description of the drawings
Fig. 1 is simulation (theory) and the experiment PXRD figures of the metal-organic framework.
Fig. 2 is the secondary construction unit figure of the metal-organic framework.
Fig. 3 is the connection mode figure of the metal-organic framework.
Fig. 4 is the three dimensional structure diagram of the metal-organic framework.
Fig. 5 is that the stability study PXRD of the metal-organic framework materials schemes.
Fig. 6 is the 77K nitrogen adsorption isotherm figures of the metal-organic framework at different conditions.
Embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
By organic ligand H4TPP (0.035 mM) and S tetra- is hydrated nickel acetate (0.035 mM) in 1mL N, N- bis-
It is well mixed in NMF, adds 0.05mL triethylamines and 0.05mL water, is enclosed in bottle.Via hot anti-at 100 DEG C
Answer 48 hours and obtain the crystal of the metal-organic framework.
Embodiment 2
By organic ligand H4TPP (0.035 mM) is with four hydration nickel acetates (0.035 mM) in 1.5mL N, N-
It is well mixed in dimethylformamide, adds 0.05mL triethylamines and 0.05mL water, is enclosed in bottle.Via heat at 100 DEG C
Reaction obtains the crystal of the metal-organic framework in 48 hours.
Embodiment 3
By organic ligand H4TPP (0.035 mM) is with four hydration nickel acetates (0.035 mM) in 2.0mL N, N-
It is well mixed in dimethylformamide, adds 0.05mL triethylamines and 0.05mL water, is enclosed in bottle.Via heat at 100 DEG C
Reaction obtains the crystal of the metal-organic framework in 48 hours.
Embodiment 4
By organic ligand H4TPP (0.035 mM) is with four hydration nickel acetates (0.035 mM) in 2.0mL N, N-
It is well mixed in dimethylformamide, adds 0.1mL triethylamines and 0.05mL water, is enclosed in bottle.Via hot anti-at 100 DEG C
Answer 48 hours and obtain the crystal of the metal-organic framework.
The test result of product obtained by above-described embodiment is identical, specifically sees below：
(1) determination of crystal structure：
Sizeable powder is chosen, under 298K, utilizes PANalytical X ' Pert PRO high-resolution powder diffractions
Instrument collects data.Data Collection uses the Cu-K α through graphite monochromator monochromatization Target ray.Pass through
The softwares of Material Studio 6.0 carry out structural simulation, have then carried out refine to crystal structure with TOPAS softwares.Crystal
Learn data and be shown in Table 1.
The crystallographic data of the metal-organic framework materials of table 1
Fig. 2 structure chart shows：The metal-organic framework includes the secondary construction unit (SBU) by eight core Ni：
Ni8O6N24.Wherein eight nickle atoms connect 6 μ4- O forms a Ni8O6Core, one preferably Ni8 cubes is finally constructed
Body, this cubical summit are occupied by nickle atom, and six faces are by 6 μ4- O is covered.Each cubical side of Ni8 and come from
Pyrazoles in porphyrin, which is connected, has finally given [Ni8O6(N2)12]12+Secondary construction unit.
Fig. 3 structure chart shows：In the metal-organic framework, each SBU passes through tetradentate ligandses (TPP4-) and surrounding ten
Two SBUs are connected.Belong to 12 connection nickel metal-organic frameworks.
Fig. 4 structure chart shows：A kind of cubical cage structure in the metal-organic framework be present.Its length of side is about
ForThe connected mode of these cage structures is by sharing TPP4-The side of part.
(2) sign of ultrastability
The stability of metal-organic framework materials is determined by PXRD；Operating procedure：By 10mg, the material is immersed in respectively
0.01mM HCl soak 24h, 0.1mM HCl and soak 24h at room temperature, soaked in 1M sodium hydroxide solutions at 100 DEG C at room temperature
24h, soaked in 10M sodium hydroxide solutions at 100 DEG C soak 24h in 24h and 100 DEG C of saturation sodium hydroxide solution after determine.
Metal-organic framework materials characterize the feature of its porosity with 77K nitrogen adsorptions under different acid-base conditions；Operation
Step is：Take respectively 60mg activate after new material, be immersed in 0.1M hydrochloric acid 24h at room temperature, saturation sodium hydroxide is molten at 100 DEG C
The nitrogen adsorption done after 24h is soaked in liquid to characterize.
Fig. 5 is the PXRD figures that invention material is tested under different electrochemical conditions, it can be seen that the material is in acid solution, alkali soluble
Good stability and crystallinity are kept in liquid.
Fig. 6 is that new synthetic sample, the 0.1mM HCl of material of the present invention soak 100 DEG C of 24h and saturation sodium hydroxide at room temperature
77K nitrogen adsorption isotherms after lower immersion 24h.It can be seen that the material is kept in different acid-base solutions
Complete porosity, the maximum N of the material2Adsorbance is 520cm3/ g, the specific surface area calculated with it (BET) are 1339m2/
g。
Claims (3)
1. a kind of metal-organic framework materials of three-dimensional porphyryl, it is characterised in that be made up of metallic nickel and porphyrin part
Metal-organic framework materials, chemical molecular formula are [Ni9.77C56.64N21.24O10.92H35.47], its mesoporphyrin part 5,10,15,
20- tetra- (1 hydrogen-pyrazoles -4- bases) porphyrin (H4TPP structural formula) is as follows：
The angle constructed from skeleton connection, the 3-dimensional metal organic framework material
Crystal structure belongs to cubic system, space group Pm-3m, and cell parameter is：A=b=c=15.4292 (9)α=β=γ
=90 °；The metal-organic framework includes the secondary construction unit (SBU) by eight core Ni：Ni8O6N24, wherein eight nickle atoms connect
Meet 6 μ4- O forms a Ni8O6Core, a Ni is finally constructed8Cube, this cubical summit are accounted for by nickle atom
Have, each face is by a μ4Nickel of-the O respectively with its four summits is connected, and six faces are by 6 μ4- O is covered；Ni8It is cubical every
Two Ni are connected by the pyrazoles in porphyrin on one side, have finally given [Ni8O6(N2)12]12+Secondary construction unit；Each
SBU passes through tetradentate ligandses (TPP4-) be connected with 12 SBUs of surrounding；In the metal-organic framework, exist a kind of SBU and
Tetradentate ligandses (TPP4-) form cubical cage structure, its length of side be 12.1These cube cage structures pass through altogether
Use TPP4-The side of part is connected so as to constitute the skeleton structure of three-dimensional；
The method of the metal-organic framework materials of three-dimensional porphyryl, comprises the following steps：Under air-proof condition, organic ligand H4TPP
(5,10,15,20- tetra- (1 hydrogen-pyrazoles -4- bases) porphyrin) and four hydration nickel acetate (Ni (OAc)2·4H2O) in DMF (N, N- diformazans
Base formamide), in the mixed solution of water and triethylamine, the crystal of the metal-organic framework is obtained via solvent thermal reaction.
2. the metal-organic framework materials of a kind of three-dimensional porphyryl according to claim 1, it is characterised in that from topology angle
Degree is seen, by the SBU, [Ni of eight core nickel8O6(N2)12] node of 12 connections is simplified to, by tetradentate ligandses TPP4-It is simplified to four companies
The node connect, whole skeleton can be simplified to the net of 4,12 connections, and its Shi Laifuli symbol is (436·630)(44·62)3, category
In the topology of ftw types.
A kind of 3. metal-organic framework materials of three-dimensional porphyryl according to claim 1, it is characterised in that characterized in that,
Organic ligand H4TPP (5,10,15,20- tetra- (1 hydrogen-pyrazoles -4- bases) porphyrin) and four hydration nickel acetates mol ratio are 1:(1~
5), every 0.05 mM of four hydration nickel acetates correspond to 0.5mL~4mL DMF, and the three of 0.2mL~2mL
Ethamine, 0.005~0.05mL water；The temperature of the thermal response is 60 DEG C -120 DEG C, and the reaction time is 40-100 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510669999.3A CN105294705B (en) | 2015-10-13 | 2015-10-13 | The porphyryl metal-organic framework materials and synthetic method of a kind of ultrastability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510669999.3A CN105294705B (en) | 2015-10-13 | 2015-10-13 | The porphyryl metal-organic framework materials and synthetic method of a kind of ultrastability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105294705A CN105294705A (en) | 2016-02-03 |
| CN105294705B true CN105294705B (en) | 2018-03-30 |
Family
ID=55192611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510669999.3A Expired - Fee Related CN105294705B (en) | 2015-10-13 | 2015-10-13 | The porphyryl metal-organic framework materials and synthetic method of a kind of ultrastability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105294705B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2013119647A (en) * | 2010-09-27 | 2014-11-10 | Те Риджентс Оф Те Юниверсити Оф Калифорния | CONDUCTING OPEN FRAME FRAME STRUCTURES |
-
2015
- 2015-10-13 CN CN201510669999.3A patent/CN105294705B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105294705A (en) | 2016-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105294705B (en) | The porphyryl metal-organic framework materials and synthetic method of a kind of ultrastability | |
| An et al. | Metal-adeninate vertices for the construction of an exceptionally porous metal-organic framework | |
| ES2703849B2 (en) | Zeolitic iron imidazolate framework, process for obtaining and nanocomposite derived from it | |
| He et al. | Metal‐organic frameworks for CO2 chemical transformations | |
| Guo et al. | Amorphous cobalt phosphate porous nanosheets derived from two-dimensional cobalt phosphonate organic frameworks for high performance of oxygen evolution reaction | |
| CN104151335B (en) | A kind of metal-organic framework material to ph stability and its preparation method and application | |
| Chen et al. | Stable amide-functionalized metal–organic framework with highly selective CO2 adsorption | |
| CN109776504A (en) | A kind of metal-organic framework material and preparation method and applications based on low symmetrical pyrazoles-Carboxylic acid ligand Zn | |
| CN107740135A (en) | A kind of hollow polyhedral preparation method and applications of meso-hole structure NiCoS | |
| Liu et al. | Trifunctional metal–organic framework catalyst for CO2 conversion into cyclic carbonates | |
| CN108774323A (en) | A kind of metal-organic framework materials and preparation method and applications of the Zr based on four tooth Carboxylic acid ligands | |
| Zhang et al. | A multifunctional Zr-MOF for the rapid removal of Cr 2 O 7 2−, efficient gas adsorption/separation, and catalytic performance | |
| Khan et al. | Novel amine functionalized metal organic framework synthesis for enhanced carbon dioxide capture | |
| Hawes et al. | Hysteretic carbon dioxide sorption in a novel copper (II)-indazole-carboxylate porous coordination polymer | |
| Si et al. | Enhancing proton conductivity in Zr-MOFs through tuning metal cluster connectivity | |
| CN107286185A (en) | A kind of cadmium metal organic framework material and preparation method thereof | |
| Li et al. | Surface-halogen-introduced 2D NiCo bimetallic MOFs via a modulation method for elevated electrochemical glucose sensing | |
| CN105753845B (en) | A kind of metal-organic framework materials and preparation method thereof based on low symmetrical four teeth Pyrazole Ligands Ni | |
| Wang et al. | A heterometallic metal–organic framework based on multi-nuclear clusters exhibiting high stability and selective gas adsorption | |
| CN106669738A (en) | Multi-element hollow metal sulfide hydrogen evolution catalyst, preparation method and application | |
| Li et al. | Core-shell NiO/C@ NiFe-LDH nanocomposite as an efficient electrocatalyst for oxygen evolution reaction | |
| Wang et al. | New challenge of microporous metal-organic frameworks for adsorption of hydrogen fluoride gas | |
| CN108997587A (en) | It is a kind of for water electrolysis hydrogen production reaction metal-organic framework material and its nanometer sheet material preparation method | |
| Park et al. | Capture instead of release: defect-modulated radionuclide leaching kinetics in metal–organic frameworks | |
| Song et al. | Fabrication of three-dimensional printed hybrid graphene oxide/calcium alginate network by 3D printing technology with outstanding U (VI) recycling capacity in acidic solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180330 Termination date: 20201013 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |