CN108586230A - Based on Cu (II) metal-organic framework materials and its synthetic method and application - Google Patents
Based on Cu (II) metal-organic framework materials and its synthetic method and application Download PDFInfo
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- CN108586230A CN108586230A CN201810360802.1A CN201810360802A CN108586230A CN 108586230 A CN108586230 A CN 108586230A CN 201810360802 A CN201810360802 A CN 201810360802A CN 108586230 A CN108586230 A CN 108586230A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
- C07C63/72—Polycyclic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to based on Cu (II) metal-organic framework material preparation and electrocatalytic hydrogen evolution performance, belong to field of catalyst preparation.The chemical molecular formula of the metal-organic framework material is：[Cu(hfipbb)(H2hfipbb)0.5]nWherein n is the natural number of non-zero, H2Hfipbb indicates 2,2 bis- (4 carboxyl phenyl) hexafluoropropane.It crystallizes in monoclinic system, belongs to P2/n space groups.The advantages that this metal-organic framework material has synthesis temperature mild, and the reaction time is short, and synthesis technology is simple and catalyst amount is few, and show that the material has higher catalytic performance in terms of electro-catalysis via test.
Description
Technical field
The invention belongs to be catalyzed preparation field, it is particularly based on Cu (II) metal-organic framework materials and its synthetic method and answers
With.
Background technology
With the continuous development of society, people are also more and more to the use of fossil fuel, enjoy its bring it is good
When place, excessively air pollution and global warming are also exacerbated using fossil fuel.Therefore, a kind of clean regenerative resource is developed
Substitute fossil fuels are a very urgent things.And Hydrogen Energy is because of its cleaning, sustainable and combustion heat value is high is considered as
One of ideal alternative energy source.Electro-catalysis is as a kind of not only simple but also efficient production hydrogen mode, it has also become domestic and international research hotspot.
So far, Pt is considered as optimal elctro-catalyst.However, the scarcity of noble metal and high cost greatly hinder
Their practical application.Therefore, the trend that cheap, sustainable and efficient elctro-catalyst becomes inevitable is found.And transition is golden
Belong to copper (Cu) and has become one of the base metal for preparing efficient HER elctro-catalysts.
The metal-organic framework material constructed is cooperateed with by organic ligand and inorganic metal center (metal ion or metal cluster)
(MOFs) cause extensive concern, be a kind of novel porous materials with the fastest developing speed in recent years, catalysis, energy storage and
It is all widely used in separation.Compared with traditional material, MOFs because with structure can design and cut-out, specific surface area be high, aperture can
The advantages that tune, it is considered to be one of most promising material.As elctro-catalyst, MOFs materials have following notable spy
Property：(1) metal active centres containing abundant unsaturated coordination in MOFs frames and big specific surface area, are the biography of electronics
It is defeated that a large amount of active site is provided；(2) the easy functionalization of MOFs materials can improve leading for material itself by modifying some functional groups
Electrically；(3) pore structure of MOFs enables it easily to be combined with other catalytic active centers, multiple to construct novel MOFs
Condensation material catalyst.Although MOFs materials embody many advantages in terms of as elctro-catalyst, there is also some problems,
Such as the disadvantage that electric conductivity is poor.
Invention content
In view of the above problems, present invention aims at a kind of Cu-MOFs is synthesized, using the catalytic performance of the MOFs materials,
Realize efficient production hydrogen effect.
To achieve the above object, the present invention takes following technical solution：
A kind of organic ligand H for synthesizing metal-organic framework material2Hfipbb, chemical name 2, the bis- (4- of 2-
Carboxyl phenyl) hexafluoropropane, chemical structural formula is：
A kind of Cu (II) metal-organic framework materials and its synthetic method and application, chemical molecular formula are：[Cu
(fipbb)(H2hfipbb)0.5]n, n is the natural number of non-zero.The basic unit of the metal-organic framework material includes 1 crystalline state
Learn independent Cu2+Ion and 1.5 organic ligands, wherein Cu2+6 carboxyl oxygen atoms on ion and 1.5 organic ligands
It is connected.Its mono-crystalline structures is as shown in Figure 1.Cu-MOFs crystallizations as shown in Figure 1 belong to monoclinic system, belong to P2/n space groups, structure cell
Parameter is：α=90 °, β=107.638 (2) °, γ=90 °,Actual crystal data are shown in Table 1.
Table 1：The crystallographic data of metal-organic framework material
The synthetic method of above-mentioned Cu (II) metal-organic framework materials Cu-MOFs, includes the following steps：In closed item
Under part, organic ligand is with cuprous iodide in DMF and H2Hydro-thermal reaction is carried out in the mixed system of O, and a certain amount of fluorine boron is added
Acid-conditioning solution pH value obtains metal-organic framework material, i.e. Cu-MOFs materials after reacting a period of time.Wherein, organic ligand
Molar ratio with cuprous iodide is 1:2-5, DMF and H2The molar ratio of O is 1:The pH=3- that fluoboric acid adjusts solution is added in 1-2
5, reaction time 20-30h, reaction temperature are 70-100 DEG C.
A kind of copper base metal organic framework materials (Cu-MOFs) elctro-catalyst being prepared by above-mentioned either step.
A kind of copper base metal organic framework materials (Cu-MOFs) elctro-catalyst is reacted applied to electrocatalytic hydrogen evolution.
This experiment also provides a kind of technical method of electro-catalysis, and the Cu-MOFs for weighing 10mg is put into weighing tube, is added
The Nafion and H of 2mL2O (V/V=1:9), it is made to be completely dispersed to obtain suspension after ultrasonic 30min, 5 μ L is taken to drop to glass later
On carbon electrode, after its drying, in 0.5M H2SO4It is tested in solution system.As a comparison, the 20%Pt/C of business is also same
Sample operates.
This experiment has the following advantages due to taking above technical scheme：
(1) synthetic method of the metal-organic framework material is simple, and the reaction time is short, and reaction temperature is mild, and no other add
Add agent, there is excellent reproducibility, and yield is high；
(2) organic ligand for constructing Cu-MOFs materials contains there are six fluorine atom, and fluorine has the electric conductivity of MOFs materials
Facilitation, and the material the fluorine atom on the faces ac show as arranged opposite and for straight-chain the characteristics of (such as Fig. 2), more
Promote the transmittability of electronics.Therefore the MOFs materials constructed using fluorine-containing organic ligand, the electric conductivity of material can be promoted,
Substantially increase electro-catalysis HER performances；
(3) this Cu-MOFs material shows the feature (such as Fig. 2) that copper metal node is arranged on a chain on the faces ac,
And such feature effectively can provide active site for electron-transport, accelerate the transmission of electronics, be conducive to the progress of evolving hydrogen reaction.
(4) metal-organic framework material great application prospect in terms of efficient electrocatalytic hydrogen evolution reaction.
For Cu-MOFs materials prepared by this method in electro-catalysis HER tests, Tafel slopes are 97mV/decade, starting
Current potential is down to for 29mV, current density 10mA/cm2When overpotential be 128mV.Property of this performance close to business 20%Pt/C
Can, therefore the present invention has prepared the efficient catalyst instead of precious metal material, which has prepared excellent for electrolysis water liberation of hydrogen
Good efficient catalyst.
Description of the drawings
Fig. 1 is the coordination context diagram of embodiment 1Cu-MOFs.
Fig. 2 is the directions the ac environment map of embodiment 1Cu-MOFs.
Fig. 3 is the thermal stability weight-loss curve of embodiment 1Cu-MOFs.
The X-ray diffractogram that Fig. 4 is embodiment 1Cu-MOFs and simulation X-ray diffractogram comparison diagram.
Fig. 5 is the infrared absorpting light spectra of embodiment 1Cu-MOFs and organic ligand.
Fig. 6 is the LSV comparison diagrams of embodiment 1Cu-MOFs and business 20%Pt/C.
Fig. 7 is the Tafel comparison diagrams of embodiment 1Cu-MOFs and business 20%Pt/C.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies within the scope of case.After reading the present invention, modification of the those skill in the art related to the various equivalent forms of the present invention
The application the attached claims are fallen within to limit in range.
Embodiment 1
In confined conditions, 0.02mmol organic ligands H is weighed2Hfipbb, 0.08mmol cuprous iodide are dissolved in N ' N-
(2mL DMF, 2mL H in the mixed solution of dimethylformamide and water2O), it is added in vial, adds fluoboric acid tune
PH value of solution=4 are saved, ultrasound uniformly obtains mixed solution, reacts for 24 hours at a temperature of 80 DEG C in baking oven, naturally cooled to after taking-up
Room temperature obtains blue-tinted transparent reguline metal organic framework materials [Cu (fipbb) (H2hfipbb)0.5]n, i.e. Cu-MOFs.Pass through
Cu-MOFs shapes, the size that this ratio and condition are prepared are uniform, and are (such as Fig. 4) to match with the XRD of crystal simulation.
Embodiment 2
In confined conditions, 0.02mmol organic ligands H is weighed2Hfipbb, 0.04mmol cuprous iodide are dissolved in N ' N-
(1mL DMF, 2mL H in the mixed solution of dimethylformamide and water2O), it is added in vial, adds fluoboric acid tune
PH value of solution=3 are saved, ultrasound uniformly obtains mixed solution, reacts 20h at a temperature of 80 DEG C in baking oven, naturally cooled to after taking-up
Room temperature obtains blue-tinted transparent reguline metal organic framework materials [Cu (fipbb) (H2hfipbb)0.5]n, i.e. Cu-MOFs.Pass through this
Cu-MOFs yields prepared by condition are relatively low, but match with the XRD of crystal simulation.
Embodiment 3
In confined conditions, 0.02mmol organic ligands H is weighed2Hfipbb, 0.1mmol cuprous iodide are dissolved in N ' N-
(2mL DMF, 2mL H in the mixed solution of dimethylformamide and water2O), it is added in vial, adds fluoboric acid tune
PH value of solution=5 are saved, ultrasound uniformly obtains mixed solution, reacts 30h, natural cooling after taking-up at a temperature of 100 DEG C in baking oven
To room temperature, blue-tinted transparent reguline metal organic framework materials [Cu (fipbb) (H is obtained2hfipbb)0.5]n, i.e. Cu-MOFs.Pass through
Cu-MOFs yields prepared by this condition are relatively low, and crystal very little, but match with the XRD of crystal simulation.
Embodiment 4
In confined conditions, 0.02mmol organic ligands H is weighed2Hfipbb, 0.06mmol cuprous iodide are dissolved in N ' N-
(1mL DMF, 2mL H in the mixed solution of dimethylformamide and water2O), it is added in vial, adds fluoboric acid tune
PH value of solution=3 are saved, ultrasound uniformly obtains mixed solution, reacts for 24 hours at a temperature of 70 DEG C in baking oven, naturally cooled to after taking-up
Room temperature obtains blue-tinted transparent reguline metal organic framework materials [Cu (fipbb) (H2hfipbb)0.5]n, i.e. Cu-MOFs.Pass through this
Cu-MOFs yields prepared by condition are relatively low, and purity is relatively low, but match with the XRD of crystal simulation.
Embodiment 5
In confined conditions, 0.02mmol organic ligands H is weighed2Hfipbb, 0.08mmol cuprous iodide are dissolved in N ' N-
(1mL DMF, 2mL H in the mixed solution of dimethylformamide and water2O), it is added in vial, adds fluoboric acid tune
PH value of solution=3 are saved, ultrasound uniformly obtains mixed solution, reacts 28h at a temperature of 80 DEG C in baking oven, naturally cooled to after taking-up
Room temperature obtains blue-tinted transparent reguline metal organic framework materials [Cu (fipbb) (H2hfipbb)0.5]n, i.e. Cu-MOFs.Pass through this
Cu-MOFs crystal prepared by condition is smaller, but matches with the XRD of crystal simulation.
Embodiment 6
The Cu-MOFs samples 10mg for weighing embodiment 1 is put into weighing tube, and the Nafion and H of 2mL is added2O (V/V=1:
9), it is made to be completely dispersed to obtain suspension after ultrasonic 30min, 5 μ L is taken to drop on glass-carbon electrode later, after its drying,
0.5M H2SO4It is tested in solution system.As a comparison, the 20%Pt/C of business is similarly operated.
Claims (6)
1. a kind of organic ligand H for synthesizing metal-organic framework material Cu-MOFs2Hfipbb, which is characterized in that its chemistry
Bis- (4- carboxyl phenyls) hexafluoropropane of 2,2- are named as, chemical structural formula is：
2. a kind of metal-organic framework material Cu-MOFs, characterized in that the metal-organic framework material, which is 3-dimensional metal, machine frame
Frame material, chemical molecular formula are：[Cu(fipbb)(H2hfipbb)0.5]n, n is the natural number of non-zero；It crystallizes in monoclinic system,
Belong to P2/n space groups, cell parameter is：α=90 °, β=107.638 (2) °, γ=90 °,
3. the synthetic method of metal-organic framework material Cu-MOFs as claimed in claim 2, characterized in that including walking as follows
Suddenly：In confined conditions, organic ligand H2Hfipbb and cuprous iodide (CuI) are dissolved in the mixed of N ' dinethylformamides and water
It closes in solution, adds fluoboric acid and adjust pH value of solution, ultrasound uniformly obtains mixed solution；Mixture is put in baking oven and is reacted,
Cooled to room temperature after taking-up obtains blue bulk crystals, i.e. metal-organic framework material [Cu (fipbb)
(H2hfipbb)0.5]n, it is named as Cu-MOFs.
4. the synthetic method of metal-organic framework material Cu-MOFs according to claim 3, which is characterized in that wherein 2,
Bis- (4- carboxyl phenyls) hexafluoropropane of 2- and the molar ratio of cuprous iodide are 1:2-5, DMF and H2The molar ratio of O is 1:1-2 adds
Enter the pH=3-5 that fluoboric acid adjusts solution, reaction time 20-30h, reaction temperature is 70-100 DEG C.
5. copper base metal organic framework materials (Cu-MOFs) are prepared according to any one of claim 3 and 4 preparation method
Elctro-catalyst.
6. copper base metal organic framework materials (Cu-MOFs) elctro-catalyst that claim 5 is prepared is on electrocatalytic hydrogen evolution
Application.
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| CN107501088A (en) * | 2017-08-04 | 2017-12-22 | 三峡大学 | A kind of preparation and its application of copper base metal organic framework materials |
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-
2018
- 2018-04-20 CN CN201810360802.1A patent/CN108586230A/en active Pending
Patent Citations (5)
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| WO2012044402A1 (en) * | 2010-09-29 | 2012-04-05 | Conocophillips Company-Ip Services Group | High-pressure quartz crystal microbalance |
| US20120247328A1 (en) * | 2011-04-04 | 2012-10-04 | Georgia Tech Research Corporation | Mof nanocrystals |
| CN105542751A (en) * | 2015-12-11 | 2016-05-04 | 广东工业大学 | Metal organic framework material capable of emitting white light, and synthetic method and application thereof |
| CN107501088A (en) * | 2017-08-04 | 2017-12-22 | 三峡大学 | A kind of preparation and its application of copper base metal organic framework materials |
| CN107602592A (en) * | 2017-10-25 | 2018-01-19 | 青岛大学 | One kind separation CO2Metal-organic framework material and preparation method thereof |
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| Title |
|---|
| CANTWELL G. CARSON ET AL.: "Sonochemical Synthesis and Characterization of Submicrometer Crystals of the Metal_Organic Framework Cu[(hfipbb)(H2hfipbb)0.5]", 《CRYST. GROWTH DES.》 * |
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