A kind of preparation method of different valence state cobalt-carbon serial nano composite material
Technical field
The invention belongs to technical field of composite preparation, and in particular to a kind of different valence state cobalt-carbon serial nano is compound
Material and preparation method thereof.
Background technology
With the continuous growth to advance with world population of social economy, 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.Utilize solar energy, wind energy
A kind of clean energy resource can effectively reduce the dependence to fossil fuel.It is but efficient due to the intermittence of these clean energy resourcies
Energy carrier and energy conversion become required and vital condition for the large-scale application of this kind of clean energy resource.Hydrogen is
A kind of preferable energy carrier because it have the characteristics that it is efficient, inexpensive, sustainable and environmental-friendly, obtained extensively
Application.Fuel cell is preferable energy conversion device, has also obtained widely research and the application of part.Photocatalytic water,
Particularly electrolysis water inexpensively prepares one of important means and most effectual way of hydrogen as realization industrialization, however slowly analyses
Oxygen reaction (OER) dynamic process significantly limits the efficiency of water decomposition, adds the consumption of energy.And fuel cell is slow
Slow Cathodic oxygen reduction (ORR) dynamic process also significantly limits energy conversion efficiency.
Commercial oxygen-separating catalyst is mainly IrO at present2And RuO2Noble metals are waited, your gold business-purpose fuel cell catalyst is
Belong to Pt, their fancy prices and rare reserves constrain the development of new energy storage and conversion, therefore, find cheap
Become the hot spot of Recent study with the non-precious metal catalyst of rich reserves.
Nano-complex particle catalytic performance is good, particularly in electro-catalysis field, is widely used in improving hydrolysis or fuel electricity
Pond electro-catalysis efficiency.With the development of synthetic technology, it has been found that the compound of transition metal and carbon becomes electrolysis water reaction and urges
The promising candidate material of agent, particularly cobalt-carbon composite, had both played the good electro catalytic activity of cobalt-based itself,
Metal is wrapped with the carbon of different graphitization degree degree again, the catalytic activity of compound interface is further improved, enhances catalysis
The stability of agent.As multi-functional cobalt-C catalyst, how simply and effectively to obtain different valence state cobalt-carbon composite is this
Class catalyst obtains the premise of large-scale application.And zeolite imidazole metalloid organic frame (MOFs) base novel complex carbon material is led
It is electrically good to ensure the homodisperse of active site again, and such material preparation process is simple, of low cost, the place of MOFs
Manage bar part slight changes can obtain different valence state cobalt-carbon serial nano composite material.Raw material of the present invention is easy to get, preparation process
Process is simple, and surfactant, precipitating reagent etc. is not required, and production cost is low, therefore this work is for developing cheap metal/carbon
Nanocomposite is used as the novel electro-catalytic material of analysis oxygen catalysis (OER) and hydrogen reduction catalysis (ORR), and realizes scale reality
Border application has far-reaching significance.
The content of the invention
The object of the present invention is to provide a kind of efficiently feasible, inexpensive different valence state cobalt-carbon serial nano composite materials
Preparation method, this method can realize that homogeneous raw material changes simultaneously to a variety of cobalts-carbon nano-composite material, i.e., with smaller cost
The purpose of cobalt carbon nano-composite material product diversification is realized with simple mode.
The specific technical solution that the present invention takes is:
1) synthesis material includes cobalt nitrate (or cobaltous sulfate or cobalt acetate or cobalt chloride), methylimidazole (or second butyl front three
Base imidazoles), sodium borohydride (or sodium hydrogen selenide).
2) by cobalt salt and imidazoles organic ligand (molar ratio 1 in proportion:1-1:5) (the v in ethanol water:V=1:1-1:4)
It is uniformly mixed;By mixed solution stirring at normal temperature 30 minutes, 10-24h is stored at room temperature, the product of generation has for zeolite imidazole metalloid
Machine frame frame material, the presoma unified as different valence state cobalt-carbon serial nano composite material is former after washed, filtering and drying
Material.
3) homogeneous raw material, the preparation of multiple product is using high temperature pyrolytic cracking (HTP) (heating temperature 600-900 degree keeps the temperature 2-6h), hydro-thermal
Carbonizatin method (heating temperature 120-180 degree, keep the temperature 5-15h) or two methods are used in conjunction realizations, and sodium borohydride (or selenium hydrogenates
Sodium) it can also assist in as reducing agent and play the role of adjusting different valence state cobalt constituent in cobalt-carbon nano-composite material, also
The adding proportion and addition manner of former agent be:50mg zeolite imidazole metalloid organic framework materials presomas are placed in ethanol water
In (v:V=1:1-1:4) disperse, add sodium borohydride (or sodium hydrogen selenide) aqueous solution 1mL-15mL (ice water of 1M-2M concentration
Bath prepare), stir 1-2min after it is spare.The forerunner's dispersion liquid for the addition reducing agent got ready is first positioned over hydrothermal reaction kettle carbon
Change, further according to needing further to be positioned over the carbonization of atmosphere furnace high temperature pyrolysis.
4) method realizes cobalt site after carbonization using the zeolite imidazole metalloid organic frame precursor material of the same race voluntarily synthesized
Be uniformly distributed with effective carbon coating, than same type of material use other synthetic methods more economically be applicable in.
Description of the drawings
Fig. 1 is different valence state cobalt-carbon serial nano composite material prepared by case study on implementation 1,2,4,5,6,7 of the present invention
X-ray diffracting spectrum;
Fig. 2 is the low power scanning transmission electronic display of cobalt-carbon serial nano composite material prepared by case study on implementation of the present invention
Micro mirror picture;
Fig. 3 is the high-resolution-ration transmission electric-lens figure of cobalt-carbon serial nano composite material prepared by case study on implementation 5 of the present invention;
Fig. 4 is the x-ray photoelectron spectroscopy point of cobalt-carbon serial nano composite material prepared by case study on implementation 5 of the present invention
Analysis figure;
Fig. 5 is the electro-catalysis oxygen evolution reaction of cobalt-carbon serial nano composite material prepared by case study on implementation 1,4,5 of the present invention
(OER) LSV contrast curves;
Specific embodiment
With reference to embodiment, the invention will be further elaborated, and these embodiments be merely to illustrate the present invention without
For limiting the scope of the invention.Simultaneously after reading the content taught by the present invention those skilled in the art to institute of the present invention
Any change or modification made, all also fall within the scope of the appended claims of the present application.
Embodiment 1:
By cobalt salt and glyoxaline ligand in molar ratio 1:3.667 in methanol and alcohol mixed solvent (v:V=1:1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It will system
Standby zeolite imidazole metalloid organic framework materials are as 600 degree of high temperature pyrolysis 3h under presoma inert atmosphere, you can obtain cobalt-
Carbon nano-composite material.
Embodiment 2:
By cobalt salt and glyoxaline ligand in molar ratio 1:3.667 in methanol and alcohol mixed solvent (v:V=1:1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It will system
Standby zeolite imidazole metalloid organic framework materials are decomposed as 140 degree of hydro-thermal 9h of presoma, you can obtain cobaltosic oxide-carbon
Nanocomposite.
Embodiment 3:
By cobalt salt and glyoxaline ligand in molar ratio 1:3.667 in methanol and alcohol mixed solvent (v:V=1:1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 3mL of 1M is stirred 5 minutes, then is positioned over 150 degree of reaction 7h of hydrothermal reaction kettle, can obtain hydroxide
Cobalt-carbon nano-composite material.
Embodiment 4:
By cobalt salt and glyoxaline ligand in molar ratio 1:3.667 in methanol and alcohol mixed solvent (v:V=1:1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 3mL of 1M is stirred 5 minutes, then is positioned over 150 degree of reaction 7h of hydrothermal reaction kettle, can obtain hydroxide
Cobalt-carbon nano-composite material.Again through tube furnace or box atmosphere furnace under protective atmosphere, the pyrolytic 2h at 700 DEG C, you can
Obtain cobalt protoxide-carbon nano-composite material.
Embodiment 5:
By cobalt salt and glyoxaline ligand in molar ratio 1:3.667 in methanol and alcohol mixed solvent (v:V=1:1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 6mL of 2M is stirred 5 minutes, then is positioned over 140 degree of reaction 9h of hydrothermal reaction kettle, can obtain cobalt-hydroxide
Sub- cobalt-carbon nano-composite material.Again through tube furnace or box atmosphere furnace under protective atmosphere, the pyrolytic 5h at 600 DEG C, i.e.,
It can obtain using cobalt as cobalt-cobalt protoxide-carbon nanometer heterogeneous composite material of main phase.
Embodiment 6:
By cobalt salt and glyoxaline ligand in molar ratio 1:3.667 in methanol and alcohol mixed solvent (v:V=1:1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 6mL of 1M is stirred 5 minutes, then is positioned over 160 degree of reaction 5h of hydrothermal reaction kettle, can obtain hydroxide
Cobalt-cobalt-carbon nano-composite material.Again through tube furnace or box atmosphere furnace under protective atmosphere, the pyrolytic 6h at 700 DEG C,
It is i.e. available using cobalt protoxide as cobalt protoxide-cobalt-carbon nanometer heterogeneous composite material of main phase.
Embodiment 7:
By cobalt salt and glyoxaline ligand in molar ratio 1:3.667 in methanol and alcohol mixed solvent (v:V=1:1) mixing in
Uniformly, mixed solution is stirred 30 minutes, be stored at room temperature for 24 hours, product washing, filtering and the 80 degree of drying for standby of generation.It weighs
50mg zeolite imidazole metalloid organic framework materials, which are placed in as presoma in 50ml ethanol waters, to be disperseed, and is added in ice-water bath
The sodium borohydride aqueous solution 1mL of 1M is stirred 5 minutes, then is positioned over 170 degree of reaction 5h of hydrothermal reaction kettle, can obtain four oxidations three
Cobalt-hydroxide cobalt-carbon nano-composite material.Again through tube furnace or box atmosphere furnace under protective atmosphere, the high temperature at 600 DEG C
Decompose 3h, you can obtain cobaltosic oxide-cobalt protoxide-carbon nanometer heterogeneous composite material.