CN107570211A - A kind of preparation method and application of cyanuro Metal-organic frame/Ni composites - Google Patents
A kind of preparation method and application of cyanuro Metal-organic frame/Ni composites Download PDFInfo
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Abstract
The application of elutriation oxygen is electrolysed the invention discloses a kind of preparation method of cyanuro Metal-organic frame/Ni composites and based on the catalyst, belongs to nano-catalytic, nano material, Metal-organic frame technical field.Cobalt nitrate aqueous solution, cyanuric acid suspension are blended its key step, and blended liquid is online coated in activated ni, under air atmosphere, are heated to 300 400 DEG C, and triazine radical Metal-organic frame nanocrystal is successfully made and is supported on the online hybrid material of activated ni.The material prepares that raw materials used cost is low, and preparation technology is simple, and energy consumption of reaction is low, has prospects for commercial application.The catalyst has efficient catalytic electrolysis water oxygen evolution activity and electrochemical stability.
Description
Technical field
It is the present invention relates to a kind of preparation method of cyanuro Metal-organic frame/Ni composites and multiple based on this
Condensation material is applied to electrolysis elutriation oxygen as catalyst；Belong to composite, catalysis technique, Metal-organic frame technology neck
Domain.
Background technology
With the high speed development of social economy and the continuous growth of world population, the mankind are to fossil fuel, such as coal and oil
Deng consumption, bring unprecedented pressure and challenge to existing energy reserves and natural environment.For the energy that reply is newborn
The requirement that source is consumed and existing population quality of life improves, countries in the world urgently search out the sustainable clean energy resource used
Carrier.The direct decomposition water of electro-catalysis, which prepares hydrogen, to be considered as realizing the process effective manner.The reaction of electrocatalytic decomposition water includes
Liberation of hydrogen (hydrogen evolution reaction, HER) and analysis oxygen (oxygen evolution reaction, OER) two
Individual half-reaction, come self-resistance, three intrinsic energy losses of aspect systems of reaction and transmission and existing catalyst price,
Factor in terms of activity and stability, it all significantly limit its popularization and extensive use.Although it is only a side reaction to analyse oxygen,
But in order to drive the power consumption penalty that oxygen evolution reaction is brought to system operation maximum, turn into the bottleneck for improving whole efficiency.Seek
New analysis oxygen elctro-catalyst cheap and easy to get and stable performance is looked for, to long term growth Hydrogen Energy, reduces environmental pollution or even alleviation generation
Energy problem in the range of boundary, there is extensive and important realistic meaning.
In the system much explored, iridium dioxide (IrO2) and ruthenic oxide (RuO2) it is considered as most effective.However,
Their rare and expensive prices, its actual application extensively is limited, therefore, developing efficient, inexpensive and earth rich content
Base metal oxygen-separating catalyst, reduce analysis oxygen electric consumption turn into an opportunities and challenges.
Inexpensive iron, cobalt, Raney nickel, it is to have reported to realize that high activity analyses the promising catalyst of oxygen.In addition, carbon-based,
Ni-based or Heteroatom doping composite is also the innovation Sexual behavior mode of oxygen-separating catalyst.In addition to material forms, catalyst
Activity it is related to its morphology.Therefore, research and development have resourceful new composition and neomorph catalyst, to realizing
High activity analysis oxygen has great importance.
Cyanuric acid is a kind of common s-triazine, and 3 nitrogen and 3 oxygen atoms are contained in its structure, is formed
Nitrogen, oxa- hexatomic ring, cyanuric acid can also exist with the resonance molecule of the diversified forms such as enol form or keto-acid, in metal combination
Substantial amounts of coordination site can be provided in the synthesis of thing, be the good part for forming Metal-organic frame.As far as we know, based on three
Paracyanogen acid and Co（II）The nano metal organic framework and its do not appeared in the newspapers in moisture parsing oxygen technology technical field that ion is formed
Road, the present invention uses a step room temperature process, by Co（Ⅱ）Cation combines with cyanuric acid coordination, then the air heat on nickel screen
Solution, have successfully been obtained cyanuro Metal-organic frame/Ni composite effective catalysts.
The content of the invention
One of technical assignment of the present invention is to make up the deficiencies in the prior art, there is provided a kind of cyanuro metal is organic
The preparation method of framework thing/Ni composites, the raw materials used cost of this method is low, and preparation technology is simple, and energy consumption of reaction is low, gained
Product property is excellent, has prospects for commercial application.
The two of the technical assignment of the present invention are to provide the use of the cyanuro Metal-organic frame/Ni composites
On the way, will the composite be used for efficient catalytic electrolysis elutriation oxygen, the catalyst have good analysis oxygen electro catalytic activity with electricity
Chemical stability.
Technical scheme is as follows：
A kind of 1. preparation method of cyanuro Metal-organic frame/Ni composites
0.48-0.68 g cobalt nitrates are dissolved in 2-3 ml distilled water, the aqueous solution of cobalt nitrate is made；By 0.20-0.32g tri-
Paracyanogen acid is blended with 4-5 mL water, ultrasonic 1min, cyanuric acid suspension is made；Two solution are shaken and are blended, take 0.10-0.15
Ml be uniformly applied to area be 0.5 cm × 1cm activated ni it is online, insert in tube furnace under air atmosphere, with 2 DEG C/min speed
Rate is warming up to 300-400 DEG C, is incubated 3h, then with 2 DEG C/min speed cooling down to room temperature, it is organic that cyanuro metal is made
Framework thing/Ni composites.
Cyanuro Metal-organic frame/Ni the composites, it is triazine radical Metal-organic frame nanocrystal
It is supported on the online hybrid material of activated ni；Triazine radical Metal-organic frame nanocrystal, chemical formula are [Co (H2L)2
(H2O)2] n, one construction unit is by a Co（II）Cation, two cyanuric acid H2L（I）Anion and two hydrones
Form；H2L（I）The structural formula of anion is as follows：
The activation nickel screen, be by nickel screen successively in acetone, absolute ethyl alcohol, distilled water respectively 2 min of ultrasound to wash away surface
Impurity, then it was aoxidized in 1 minute with the dust technology ultrasound that mass fraction is 30%, the acid on surface is then removed with distilled water, finally
Naturally dry is made at room temperature.
The nickel screen, buys in ElectroChem, surface density 280-420g/m2, aperture 0.2-0.6mm, longitudinal stretching
Intensity is 106N/cm2, transverse tensile strength 76N/cm2, porosity 97.2%.
2. cyanuro Metal-organic frame/Ni composites as described above are as electrolysis water oxygen-separating catalyst
Using
Using three-electrode electro Chemical work station, cyanuro Metal-organic frame/Ni composites are as working electrode；Pt
Piece (mm of 5 mm × 5 × 0.1 mm) is that Ag/AgCl electrodes are reference electrode, are 0.5 M KOH water in electrolyte to electrode
The water-based energy of electrocatalytic decomposition is tested in solution, as current density, J=10mA/cm2When, current potential is 1.20 V vs RHE, works as electric current
Density J=50mA/cm2When, current potential is 1.50 V vs RHE, illustrates that the material has good analysis oxygen catalytic activity；Circulation
Before and after 1000 circles, such material polarization curve does not find obvious change, shows that catalyst stability is good.
The beneficial technique effect of the present invention is as follows：
（1）Simple process, it is easy to industrialize
Cyanuro Metal-organic frame/Ni composites prepared by the present invention, it is by part melamine, Co（II）Just from
Son and aqueous solvent, one-step method is blended using shaking, gel is obtained, gel is directly loaded on nickel screen, without hydro-thermal work
Skill, directly heat, a step process is successfully realized the generation of cyanuro Metal-organic frame nanocrystal and in nickel screen
On load, the composite preparation process is simple, and easily operated, cost is low, less energy consumption, is easy to industrialize.
（2）Catalysis analysis oxygen efficiency is high and stability is good
The invention provides a kind of cyanuro Metal-organic frame/Ni composite electro-catalysis oxygen-separating catalysts, due to this
Catalyst directly as working electrode be used for be catalyzed water decomposition analysis oxygen, eliminate conventional operation electrode using perfluorinated resin or its
Its adhesive coheres fine catalyst, and Metal-organic frame nanocrystal exposes more avtive spots so that based on this
The catalysis analysis oxygen of composite, high catalytic efficiency and stability is good.
Embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not only limited to implement
Example, the change that professionals in the field is made to technical solution of the present invention, all should belong in protection scope of the present invention.
Embodiment 1
A kind of preparation method of cyanuro Metal-organic frame/Ni composites
0.48 g cobalt nitrates are dissolved in 2 ml distilled water, the aqueous solution of cobalt nitrate is made；By 0.20g cyanuric acids and 4mL
Water is blended, ultrasonic 1min, and cyanuric acid suspension is made；Two solution are shaken and are blended, take 0.10 ml to be uniformly applied to area to be
0.5 cm × 1cm activated ni is online, inserts in tube furnace under air atmosphere, is warming up to 300 DEG C with 2 DEG C/min speed, insulation
3h, then with 2 DEG C/min speed cooling down to room temperature, cyanuro Metal-organic frame/Ni composites are made.
Embodiment 2
A kind of preparation method of cyanuro Metal-organic frame/Ni composites
0.68 g cobalt nitrates are dissolved in 3 ml distilled water, the aqueous solution of cobalt nitrate is made；By 0.32g cyanuric acids and 5 mL
Water is blended, ultrasonic 1min, and cyanuric acid suspension is made；Two solution are shaken and are blended, take 0.15 ml to be uniformly applied to area to be
0.5 cm × 1cm activated ni is online, inserts in tube furnace under air atmosphere, is warming up to 300 DEG C with 2 DEG C/min speed, insulation
3h, then with 2 DEG C/min speed cooling down to room temperature, cyanuro Metal-organic frame/Ni composites are made.
Embodiment 3
A kind of preparation method of cyanuro Metal-organic frame/Ni composites
0.55 g cobalt nitrates are dissolved in 2.5 ml distilled water, the aqueous solution of cobalt nitrate is made；By 0.25g cyanuric acids with
4.5 mL water are blended, ultrasonic 1min, and cyanuric acid suspension is made；Two solution are shaken and are blended, take 0.13 ml to be uniformly applied to
Area is that 0.5 cm × 1cm activated ni is online, inserts in tube furnace under air atmosphere, 300 are warming up to 2 DEG C/min speed
DEG C, 3h is incubated, then with 2 DEG C/min speed cooling down to room temperature, cyanuro Metal-organic frame/Ni composite woods are made
Material.
Embodiment 4
Cyanuro Metal-organic frame/Ni composites described in embodiment 1-3, it is triazine radical Metal-organic frame nanometer
Crystal load is in the online hybrid material of activated ni；Triazine radical Metal-organic frame nanocrystal, chemical formula are [Co (H2L)2
(H2O)2] n, one construction unit is by a Co（II）Cation, two cyanuric acid H2L（I）Anion and two hydrones
Form；H2L（I）The structural formula of anion is as follows：
The activation nickel screen, be by nickel screen successively in acetone, absolute ethyl alcohol, distilled water respectively 2 min of ultrasound to wash away surface
Impurity, then it was aoxidized in 1 minute with the dust technology ultrasound that mass fraction is 30%, the acid on surface is then removed with distilled water, finally
Naturally dry is made at room temperature；
The nickel screen, buys in ElectroChem, and surface density is 280-420 g/m2, aperture 0.2-0.6 mm, longitudinal stretching is strong
Spend for 106 N/cm2, transverse tensile strength is 76 N/cm2, porosity 97.2%.
Embodiment 5
Cyanuro Metal-organic frame/application of the Ni composites as electrolysis water oxygen-separating catalyst
Using three-electrode electro Chemical work station, have respectively with cyanuro metal made from embodiment 1, embodiment 2 or embodiment 3
Machine frame thing/Ni composites are as working electrode；Pt pieces (mm of 5 mm × 5 × 0.1 mm) are to electrode, Ag/AgCl electricity
Extremely reference electrode, electrolyte be the 0.5 M KOH aqueous solution in test electrocatalytic decomposition it is water-based can, when current density, J=
10mA/cm2When, current potential is 1.20 V vs RHE, as current density, J=50mA/cm2When, current potential is 1.50 V vs RHE, explanation
The material has good analysis oxygen catalytic activity；Before and after the circle of circulation 1000, such material polarization curve does not find obvious
Change, shows that catalyst stability is good.
Embodiment 6
Cu (the II)-MOF, chemical formula are [Cu3L(H2O)3]·10H2O·5DMA；One construction unit is 3 Cu（II）
Cation, three hydrones and 5 DMA molecules are formed, and DMA is DMA；It is described to be based on Cu (II)-MOF/Ni
Composite, it is that hybrid material is formed by carbon point, nano cupric oxide and porous carbon, the hybrid material is supported on nickel screen and formed again
Condensation material.
Claims (4)
1. a kind of preparation method of cyanuro Metal-organic frame/Ni composites, it is characterised in that step is as follows：
0.48-0.68 g cobalt nitrates are dissolved in 2-3 ml distilled water, the aqueous solution of cobalt nitrate is made；By 0.20-0.32g tri-
Paracyanogen acid is blended with 4-5 mL water, ultrasonic 1min, cyanuric acid suspension is made；Two solution are shaken and are blended, take 0.10-0.15
Ml be uniformly applied to area be 0.5 cm × 1cm activated ni it is online, insert in tube furnace under air atmosphere, with 2 DEG C/min speed
Rate is warming up to 300-400 DEG C, is incubated 3h, then with 2 DEG C/min speed cooling down to room temperature, cyanuro metal, which is made, to be had
Machine frame thing/Ni composites.
2. the preparation method of cyanuro Metal-organic frame/Ni composites as claimed in claim 1, its feature exist
In the cyanuro Metal-organic frame/Ni composites, being that triazine radical Metal-organic frame nanocrystal is supported on
The online hybrid material of activated ni；Triazine radical Metal-organic frame nanocrystal, chemical formula are [Co (H2L)2(H2O)2] n, its
One construction unit is by a Co（II）Cation, two cyanuric acid H2L（I）Anion and two hydrones are formed；H2L（I）
The structural formula of anion is as follows：
。
3. require the preparation method of cyanuro Metal-organic frame/Ni composites described in 1, it is characterised in that described
Nickel screen is activated, is that ultrasound 2 minutes to wash away surface impurity, then is used respectively in acetone, absolute ethyl alcohol, distilled water successively by nickel screen
The dust technology ultrasound that mass fraction is 30% aoxidizes for 1 minute to it, the acid on surface is then removed with distilled water, at room temperature finally
Naturally dry is made.
4. cyanuro Metal-organic frame prepared by preparation method as claimed in claim 1/Ni composites are as electricity
Solve the application of elutriation VPO catalysts.
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| CN201710791406.XA CN107570211B (en) | 2017-09-05 | 2017-09-05 | Preparation method and application of s-triazine-based metal-organic framework/Ni composite material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108842168A (en) * | 2018-06-29 | 2018-11-20 | 太原理工大学 | A kind of two-step electrochemical method preparation g-C3N4/ MMO compound film optoelectronic pole |
| CN109134518A (en) * | 2018-08-30 | 2019-01-04 | 济南大学 | A kind of Metal-organic frame Cd-MOF crystalline material and its preparation method and application |
| CN109647408A (en) * | 2019-02-12 | 2019-04-19 | 济南大学 | A kind of preparation method and application of the porous compound self-supporting catalyst based on Co-MOF |
| CN110038637A (en) * | 2019-05-05 | 2019-07-23 | 济南大学 | Preparation method and application of ternary nanocomposite |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108842168A (en) * | 2018-06-29 | 2018-11-20 | 太原理工大学 | A kind of two-step electrochemical method preparation g-C3N4/ MMO compound film optoelectronic pole |
| CN108842168B (en) * | 2018-06-29 | 2020-06-02 | 太原理工大学 | Two-step electrochemical method for preparing g-C3N4/MMO composite film photoelectrode |
| CN109134518A (en) * | 2018-08-30 | 2019-01-04 | 济南大学 | A kind of Metal-organic frame Cd-MOF crystalline material and its preparation method and application |
| CN109647408A (en) * | 2019-02-12 | 2019-04-19 | 济南大学 | A kind of preparation method and application of the porous compound self-supporting catalyst based on Co-MOF |
| CN109647408B (en) * | 2019-02-12 | 2021-03-23 | 济南大学 | Preparation method and application of Co-MOF-based porous composite self-supporting catalyst |
| CN110038637A (en) * | 2019-05-05 | 2019-07-23 | 济南大学 | Preparation method and application of ternary nanocomposite |
| CN110038637B (en) * | 2019-05-05 | 2022-05-13 | 济南大学 | Preparation method and application of ternary nanocomposite |
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