CN107778494A - A kind of preparation method of nickel cobalt metal-organic framework materials - Google Patents
A kind of preparation method of nickel cobalt metal-organic framework materials Download PDFInfo
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Abstract
A kind of preparation method of nickel cobalt metal-organic framework materials, belong to the preparing technical field of nano material.Glutaric acid and potassium hydroxide are dissolved in organic solution, form solution A；Cobalt salt and nickel salt are dissolved in water and ethanol solution, form solution B；Solution A and solution B are mixed into laggard water-filling thermal response again, is then washed using water and ethanol, is taken solid phase to dry, produce nickel cobalt metal-organic framework materials.For the present invention using the nickel cobalt metal-organic framework materials of the nontoxic a series of high quality of Material synthesis, reasonable in design, mild condition, easy to operate, cost is cheap, and repeatability is high, is adapted to large-scale production and application.
Description
Technical field
The invention belongs to the preparing technical field of nano material.
Background technology
The representative form of the energy, particularly coal and oil as non-renewable energy resources, the daily life with us cease manner of breathing
Close.Come in the past few decades, substantial amounts of waste has caused the whole world to the energy in substantial amounts of pollution, the high consumption and industrial development of the energy
The concern of crisis.In post-industrial society, this crisis has had influence on the development of power industry, causes materials chemistry and grinds
That studies carefully sharply increases.In recent years, emerging, efficiently energy storage material research and development achieves continuous progress.
Metal-organic framework materials（MOF）, a kind of new porous part being made up of metal ion and cluster organic matter
Material, it has been widely studied.Various characterizing methods show that excellent bone framework and good pore structure fit MOF materials
For ultracapacitor, sensor, absorption, drug delivery etc..Compared to other ligand materials, due to large surface
Product, high porosity, low-density, controlled architecture, adjustable aperture, MOFs materials are considered as most promising in following nm regime
One of material.The size of the hole of MOFs material precursors can be tuned by changing organic ligand, maximum diameter of hole 9.8
Nanometer.
Nanobelt makes it especially sensitive to adsorption due to its big specific surface area, external environment such as temperature, concentration etc.
The change of factor can cause the change of electron transport rapidly.It can significantly be used it for using its resistance variations in ultracapacitor,
The defects of MOF structural conductive differences can be made up.
The content of the invention
Needs based on above prior art and market, the present invention provide a series of system of nickel cobalt metal-organic framework materials
Preparation Method.
The present invention comprises the following steps：
1）By glutaric acid (C5H8O4) and potassium hydroxide (KOH) be dissolved in organic solution reaction after, obtain mixed solution A.The step
In, what glutaric acid was carried out as part bronsted lowry acids and bases bronsted lowry is neutralization reaction.
The present invention uses glutaric acid (C5H8O4) it is organic ligand, glutaric acid is common organic ligand, inexpensive and be easy to get, because
This is preferentially used.
The present invention uses water soluble alkali of the potassium hydroxide (KOH) for the present invention, in common water soluble alkali, potassium hydroxide
Stably it is easy to get and cheap, therefore pays the utmost attention to use potassium hydroxide in the present invention.
2）Cobalt salt and nickel salt are dissolved in water and ethanol solution, form solution B.
3）Above-mentioned solution A and solution B are mixed into laggard water-filling thermal response.
4）After hydro-thermal reaction terminates, washed with water and ethanol, take solid phase to dry, produce cobalt-nickel Organometallic framework material.
3）Above-mentioned solution A and solution B are mixed into laggard water-filling thermal response；
4）After hydro-thermal reaction terminates, washed using water and ethanol, take solid phase to dry, produce nickel cobalt metal-organic framework materials.
The present invention utilizes the nickel cobalt metal-organic framework materials of the nontoxic a series of high quality of Material synthesis, design conjunction
Reason, mild condition is easy to operate, and cost is cheap, and repeatability is high, is adapted to large-scale production and application.
Further, hydro-thermal reaction of the present invention is carried out under conditions of 150~200 DEG C, in 150~200 DEG C of high temperature bar
Part can increase the movement velocity of molecule, either still kinetically all accelerate reaction speed in thermodynamics, carry out reaction
More quickly and thoroughly, and can ensure that the complex pattern to be formed is optimal.
The present invention further preferably Co (NO3)2•6H2O as cobalt salt, using Ni (CH3COO)2•4H2O is nickel salt, in actual experiment
In, because nitrate anion and acetate are easily sloughed, it is more easy to obtain required product, therefore preferentially use this several nickelate.
During cobalt salt and nickel salt mixing of the present invention, the mol ratio of nickel and cobalt is 5~20: 1.The present invention is by using different proportion
Nickel salt reacted with cobalt salt, the ratio of each metal salt in final obtained material is different, can prepare material not
Same metal alloy particle.
The solution that the second alcohol and water that it is 1: 1 by volume ratio that the organic solution, which is, forms.
Brief description of the drawings
Fig. 1 is the x-ray photoelectron energy spectrum diagram of the made Ni-MOF metal-organic framework materials of embodiments of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the made Ni-MOF metal-organic framework materials of embodiments of the present invention 1.
Fig. 3 is the X ray light of metal-organic framework materials when the made nickel cobalt mol ratio of embodiments of the present invention 2 is 20: 1
Electronic energy spectrum.
Fig. 4 is the scanning electricity of metal-organic framework materials when the made nickel cobalt mol ratio of embodiments of the present invention 2 is 20: 1
Mirror figure.
Fig. 5 is the X ray light of metal-organic framework materials when the made nickel cobalt mol ratio of embodiments of the present invention 3 is 10: 1
Electronic energy spectrum.
Fig. 6 is the scanning electricity of metal-organic framework materials when the made nickel cobalt mol ratio of embodiments of the present invention 3 is 10: 1
Mirror figure.
Fig. 7 is the X ray light of metal-organic framework materials when the made nickel cobalt mol ratio of embodiments of the present invention 4 is 5: 1
Electronic energy spectrum.
Fig. 8 is the ESEM of metal-organic framework materials when the made nickel cobalt mol ratio of embodiments of the present invention 4 is 5: 1
Figure.
Fig. 9 is the x-ray photoelectron energy spectrum diagram of the made Co-MOF metal-organic framework materials of embodiments of the present invention 5.
Figure 10 is the scanning electron microscope (SEM) photograph of the made Co-MOF metal-organic framework materials of embodiments of the present invention 5.
Embodiment
The present invention will be further described for example below, but not limited to this.
The pattern of nickel cobalt metal-organic framework materials prepared by following embodiment is shown by supra-55 type scanning electrons
Micro mirror（SEM）Photo is shown.
Embodiment 1：
（1）Weigh 0.400g glutaric acid, 0.300g KOH respectively, be dissolved in 15mL by volume ratio be 1: 1 second alcohol and water group
Into solution in, obtain 15mL solution As.
（2）Weigh 0.500g nickel acetate (Ni (CH3COO)2•4H2O) be dissolved in 15mL by volume ratio be 1: 1 second alcohol and water
In the solution of composition, 15mL solution Bs are obtained.
（3）Solution B is slowly dropped in solution A, and magnetic agitation 0.5h.
（4）By step（3）In obtained solution be placed under 100~120 DEG C of environmental conditions and carry out hydro-thermal reaction 48h.
After the completion of hydro-thermal reaction, with water and ethanol repeatedly washing respectively, solid product is obtained.
Embodiment 2：
（1）Weigh 0.400g glutaric acid, 0.300g KOH respectively, be dissolved in 15mL by volume ratio be 1: 1 second alcohol and water group
Into solution in, obtain 15mL solution As.
（2）0.4762g nickel acetate (Ni (CH are weighed respectively3COO)2•4H2O), 0.0238g cobalt nitrate (Co (NO3)2•
6H2O 15mL) is dissolved in by the solution that form of second alcohol and water that volume ratio is 1: 1, acquirement 15mL solution Bs.
In above materials, the mol ratio of nickel cobalt is 20: 1.
（3）Solution B is slowly dropped in solution A, and magnetic agitation 0.5h.
（4）By step（3）In obtained solution put hydro-thermal reaction 48h carried out under 100~120 DEG C of environmental conditions.
After the completion of hydro-thermal reaction, with water and ethanol repeatedly washing respectively, solid product is obtained.
Embodiment 3：
The preparation method of nickel cobalt metal-organic framework materials, step is with embodiment 2, except that the mol ratio of nickel cobalt is 10:
1。
Embodiment 4：
The preparation method of nickel cobalt metal-organic framework materials, step is with embodiment 2, except that the mol ratio of nickel cobalt is 5:
1。
Embodiment 5：
（1）Weigh 0.3959g glutaric acid, 0.2292g KOH respectively, be dissolved in 10mL by volume ratio be 1: 1 second alcohol and water
In the solution of composition, 10mL solution As are obtained.
（2）Weigh 0.500g cobalt nitrate Co (NO3)2•6H2O is dissolved in 15mL and is made up of the second alcohol and water that volume ratio is 1: 1
Solution in, obtain 15mL solution Bs.
（3）Solution B is slowly dropped in solution A, and magnetic agitation 0.5h.
（4）By step（3）In obtained solution put hydro-thermal reaction 48h carried out under 100~120 DEG C of environmental conditions.
After the completion of hydro-thermal reaction, with water and ethanol, repeatedly washing, room temperature are dried respectively, obtain product Co-MOF.
By the x-ray photoelectron energy spectrum diagram of the made Ni-MOF metal-organic framework materials of Fig. 1 embodiments of the present invention 1
It can be seen that Ni-MOF metal-organic framework materials are only by C, tri- kinds of element compositions of O, Ni.
The content table of three kinds of elements is seen below：
From upper table：Constituent content test result ratio is with launching material than consistent.
The stereoscan photograph of Ni-MOF metal-organic framework materials can be seen that as made from Fig. 2 example 1：Ni-MOF
Metal-organic framework materials are ultrathin nanometer band structure.
By the made nickel cobalt mol ratio of Fig. 3 embodiment 2 be 20: 1 when metal-organic framework materials x-ray photoelectron energy
Spectrogram can be seen that：NiCo(20:1)-MOF metal-organic framework materials are only by C, O, Ni, tetra- kinds of element compositions of Co.
The content table of three kinds of elements is seen below：
From upper table：Constituent content test result ratio is with launching material than consistent.
Nickel cobalt mol ratio made from middle example 2 from Fig. 4 is the stereoscan photograph of 20: 1 metal-organic framework materials
It can be seen that：Products therefrom is ultrathin nanometer band structure when nickel cobalt mol ratio is 20: 1.
By the made nickel cobalt mol ratio of 5 embodiment 3 be 10: 1 when metal-organic framework materials x-ray photoelectron power spectrum
Figure can be seen that：NiCo(10:1)-MOF metal-organic framework materials are only by C, O, Ni, tetra- kinds of element compositions of Co, and test
Success ratio is with launching material than consistent.
The content table of three kinds of elements is seen below:
From upper table：Constituent content test result ratio is with launching material than consistent.
Nickel cobalt mol ratio made from example 3 from Fig. 6 is that the stereoscan photograph of 10: 1 metal-organic framework materials can
To find out：Products therefrom is ultrathin nanometer band structure when nickel cobalt mol ratio is 10: 1.
By the made nickel cobalt mol ratio of Fig. 7 embodiment 4 be 5: 1 when metal-organic framework materials x-ray photoelectron energy
Spectrogram can be seen that：NiCo(5:1)-MOF metal-organic framework materials are only by C, O, Ni, tetra- kinds of element compositions of Co, and test
Success ratio is with launching material than consistent.
The content table of three kinds of elements is seen below:
From upper table：Constituent content test result ratio is with launching material than consistent.
Nickel cobalt mol ratio made from example 3 from Fig. 8 is that the stereoscan photograph of 5: 1 metal-organic framework materials can be with
Find out：Products therefrom is ultrathin nanometer band structure when nickel cobalt mol ratio is 5: 1.
It can be seen by the x-ray photoelectron energy spectrum diagram of the made Co-MOF metal-organic framework materials of Fig. 9 embodiment 5
Go out：Co-MOF metal-organic framework materials are only by C, tri- kinds of element compositions of O, Co.
The content table of three kinds of elements is seen below:
From upper table：Constituent content test result ratio is with launching material than consistent.
The stereoscan photograph of Co-MOF nanobelt materials can be seen that as made from Figure 10 example 5：Co-MOF metals
Organic backbone is ultrathin nanometer band structure.
Comparative illustration：
Example 1 is only with nickel acetate (Ni (CH3COO)2•4H2O Ni-MOF) is made, example 5 is only with cobalt nitrate Co (NO3)2•6H2O systems
Obtain Co-MOF.Although the metal salt that two invention cases are selected is different, the final metal for being obtained for nano strip organic is matched somebody with somebody
Compound.Illustrate that the method that the present invention uses is applicable not only to the preparation of nickel-base material, while be also applied for the preparation of cobalt-based material.
And example 2,3,4 employs ratio difference nickel salt and cobalt salt, illustrate nickel salt and cobalt salt of the present invention by different proportion
Regulated and controled, final obtained different proportion, a series of nickel cobalt metal-organic framework materials.
Claims (6)
1. a kind of preparation method of nickel cobalt metal-organic framework materials, it is characterised in that comprise the following steps：
1）Glutaric acid and potassium hydroxide are dissolved in organic solution, form solution A；
2）Cobalt salt and nickel salt are dissolved in water and ethanol solution, form solution B；
3）Above-mentioned solution A and solution B are mixed into laggard water-filling thermal response；
4）After hydro-thermal reaction terminates, washed using water and ethanol, take solid phase to dry, produce nickel cobalt metal-organic framework materials.
2. preparation method according to claim 1, it is characterised in that the temperature conditionss of the hydro-thermal reaction are 150~200
℃。
3. preparation method according to claim 1, it is characterised in that during cobalt salt and the nickel salt mixing, mole of nickel and cobalt
Than for 5~20: 1.
4. according to the preparation method described in claim 1 or 2 or 3, it is characterised in that the cobalt salt is Co (NO3)2•6H2O。
5. according to the preparation method described in claim 1 or 2 or 3, it is characterised in that the nickel salt is Ni (CH3COO)2•4H2O。
6. preparation method according to claim 1, it is characterised in that the ethanol that it is 1: 1 by volume ratio that the organic solution, which is,
With the solution of water composition.
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Citations (5)
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| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
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| CN106770544A (en) * | 2016-11-29 | 2017-05-31 | 扬州大学 | Ni MOF ultrathin nanometers band, synthetic method and its application |
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2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101306664B1 (en) * | 2011-12-16 | 2013-09-10 | 한국생산기술연구원 | Catalyst composition for fuel cells to substitute platinium catalyst |
| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
| CN104362306A (en) * | 2014-09-19 | 2015-02-18 | 中国科学院宁波材料技术与工程研究所 | Chain-like bidentatum dicarboxylic acid-metallic composite material and preparation and application thereof |
| CN106770544A (en) * | 2016-11-29 | 2017-05-31 | 扬州大学 | Ni MOF ultrathin nanometers band, synthetic method and its application |
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